Polymers of self- and diol reactive formaldehyde-free crosslinking monomers

ABSTRACT

A compound represented by the following formula:  turated organic radical having functionality which renders the nitrogen atom electron deficient, the olefinic unsaturation functionality being polymerizable, R1 is hydrogen or a C1-C4 alkyl radical, or R and R1 together with the nitrogen atom can form an olefinically unsaturated 5 to 7-member ring which has functionality that renders the nitrogen atom electron deficient and the olefinic unsaturation functionality is polymerizable, R2 and R3 are hydrogen, a C1-C4 alkyl or acyl radical, or R2 and R3 together are a C2-C4 alkylene group, R4 is hydrogen or a C1-C4 alkyl, acyl, ester, amide or acid group, and n is an integer from 1 to 10, provided n is not 1 when R is (meth)acryloyl, R2 and R3 are methyl and R1 and R4 are hydrogen. Under acidic conditions the above compounds in which R1 is hydrogen afford cyclic hemiamidals and hemiamide ketals of the following formula:   &lt;IMAGE&gt;   The dialkyl acetal and ketal compounds and the cyclic hemiamidal and hemiamide ketal compounds can be homopolymerized or polymerized with other copolymerizable monomers.

This is a continuation of application Ser. No. 07/728,773 filed on 8Jul. 1991, now abandoned, which is a continuation of U.S. Ser. No.07/471,146 filed 26 Jan. 1990, now abandoned, which is a continuation ofU.S. Ser. No. 06/762,977 filed 6 Aug. 1985, now abandoned.

TECHNICAL FIELD

The present invention relates to olefinically unsaturated monomers whichcan self-crosslink or react with hydroxy-containing crosslinking agentsand can also be incorporated into polymers by free radical addition.

BACKGROUND OF THE INVENTION

Emulsion and solution polymers find wide application as adhesives,binders and coatings. Unfortunately, many of these polymeric materials,especially those prepared predominantly from vinyl acetate, ethylene,vinyl chloride, or their mixtures, show inadequate resistance to waterand other solvents in their everyday use. In particular, they experiencesubstantial and unacceptable loss in strength in the presence ofsolvents such as perchloroethylene, methyl ethyl ketone and toluene. Inaddition, many of these polymers exhibit deficiencies in adhesion to thesubstrates on which they are used, for example vinyl acetate, ethyleneor vinyl chloride polymers on glass, metal or polyester. Thesedeficiencies are reduced, especially for relatively hydrophilicmonomers, by the use of adhesion promoting or crosslinking comonomersand/or post-added crosslinkers.

By far the most successful crosslinking materials are aminoplasts,especially N-methylolacrylamide and urea-formaldehyde condensates. Thesematerials have met substantial success because they are low in cost,highly compatible with aqueous emulsion systems, rapidly cured underacid catalysis, and substrate reactive in that, for example, they reactwith the hydroxyl groups of cellulosic materials. These crosslinkingmaterials, however, suffer from two deficiencies: (1) the emission oflow levels of formaldehyde during cure and subsequent use, and (2)inadequate adhesion to certain substrates, for example, metal, glass andpolyester.

Many attempts have been made to overcome or minimize the firstdeficiency, especially after the potential carcinogenicity and irritantproperties of formaldehyde became widely recognized.

To reduce the level of formaldehyde in emulsion products, the use ofO-alkylated N-methylolacrylamides such as butoxymethylacrylamide or theuse of about equimolar ratios of N-methylolacrylamide with acrylamidewere introduced. These materials did not, however, totally eliminate thepresence of formaldehyde.

Acrylamide/glyoxylic acid condensates and their ethers and esters havebeen used. These materials have not performed well in applications withvinyl acetate-ethylene emulsions, especially on nonwoven cellulosicsubstrates. The use of amide/glutaraldehyde condensates, for example thecondensate with acrylamide, has also been attempted. The combination ofthe reagents, however, gave a complex mixture of uncharacterizableproducts which did not perform well in textile crosslinkingapplications.

Epoxide functional comonomers such as allyl glycidyl ether, glycidyl(meth)acrylate or their precursors have also been used. These compoundssuffered from high costs, limited shelf stability of the functionalizedemulsion polymer and toxicity questions associated with epoxidematerials.

Other approaches have used esterification chemistry (carboxylic acidplus alcohol to give an ester crosslink), but such approaches require aslow and expensive high temperature curing cycle. Post-addition offormaldehyde-free urea/glyoxal condensates includingN,N'-dialkyl-4,5-dihydroxyimidazoles has been used in Japan for fabrictreating but such systems are less efficient thanformaldehyde-containing analogs.

Thus there is a need for functional monomers which, after incorporationinto polymers or copolymers, can be crosslinked under mild conditionswith themselves and/or other polymer or substrate reactive groups togive binders, adhesives and/or coatings with high water and solventresistance and good substrate adhesion. Such products should also beformaldehyde-free.

SUMMARY OF THE INVENTION

There are provided N-olefinically substituted cyclic hemiamidals andhemiamide ketals, and N-olefinically substituted dialkyl acetals andketals which can be incorporated into free radical addition polymers.The resulting polymerized monomers undergo efficient acid catalyzed,thermally activated post-crosslinking with themselves or they can reactwith active hydrogen-containing comonomers of the polymers and/or withgroups on the substrate to which the polymer is applied.

The dialkyl acetal and ketal monomers of the invention can berepresented by the following general formula I: ##STR3## wherein R is aC₃ -C₂₄ olefinically unsaturated organic radical having functionalitywhich renders the nitrogen atom electron deficient, the olefinicunsaturation being polymerizable,

R¹ is hydrogen or a C₁ -C₄ alkyl radical, or

R and R¹ together with the nitrogen atom can form an olefinicallyunsaturated 5-7 member heterocyclic ring which has functionality thatrenders the nitrogen atom electron deficient,

R² and R³ are hydrogen, a C₁ -C₄ alkyl or acyl radical, or

R² and R³ together are a C₂ -C₄ alkylene group,

R⁴ is hydrogen or a C₁ -C₄ alkyl, acyl, ester, amide or acid group, and

n is an integer from 1 to 10, provided n is not 1 when R is(meth)acryloyl, R² and R³ are methyl and R¹ and R⁴ are hydrogen.

Under acidic conditions those monomers in which R¹ is hydrogen and R²and R³ do not compose an alkylene group afford N-olefinicallysubstituted cyclic hemiamidals and hemiamide ketals of the followinggeneral formula II: ##STR4## wherein R and R⁴ are as defined above, R²is hydrogen or a C₁ -C₄ alkyl or acyl group, and n is 2 to 5, provided Ris not an olefinically unsaturated amino carbonyl group when n is 1 or2.

Whenever reference is made to dialkyl acetals and cyclic hemiamidals, itis understood that dialkyl ketals and cyclic hemiamide ketals,respectively, are included.

The N-olefinically substituted cyclic hemiamidals and the dialkyl acetaland ketal monomers show especially rapid reactivity and efficientcrosslinking with diols such as polyvinyl alcohol. The resultingcrosslinked products show excellent solvent and water resistance, lowenergy cure and good adhesion for application as coatings, binders oradhesives. Foremost they contain no formaldehyde.

The two classes of compounds of the invention equilibrate under acidcatalysis with open chain aldehydes and ketones and cyclic iminium ions.The species react: (1) as normal aminoplasts with a second equivalent ofhemiamidal, i.e. self-crosslinking; (2) with active hydrogen compoundssuch as alcohols, amides, acids or amines; or (3) as aldehydes andketones with diols, especially 1,2- and 1,3-diols, to give stableacetals and ketals. Covalent attachment of the aldehyde to the nitrogenatom of the molecule prevents loss of aldehyde, for example formaldehydeemissions, and makes possible crosslinking by acetal formation.

The dialkyl acetal and ketal compounds and the cyclic hemiamidal andhemiamide ketal compounds of the invention are free radicalpolymerizable. Accordingly, another aspect of the invention comprisespolymers incorporating such compounds as polymerized monomers. Becauseof the incorporated monomers, the polymers under acid catalysis canself-crosslink and react with active hydrogen compounds such as alcoholsand diols.

DETAILED DESCRIPTION OF THE INVENTION

The dialkyl acetal and ketal monomers of the invention have thefollowing general formula I: ##STR5## wherein R is an olefinicallyunsaturated organic radical having 3 to 24 carbon atoms andfunctionality which renders the nitrogen atom electron deficient, theolefinic unsaturation being free radical polymerizable,

R¹ is H or a C₁ -C₄ alkyl radical, or

R and R¹ together with the nitrogen atom form a heterocyclicolefinically unsaturated organic radical of 5 to 7 atoms composing thering and having functionality which renders the nitrogen atom electrondeficient,

R² and R³ are independently hydrogen, a C₁ -C₄ alkyl or acyl radical, or

R² and R³ together form a C₂ -C₄ alkylene radical,

R⁴ is a C₁ -C₄ alkyl, acyl, ester, amide or acid radical, but ispreferably hydrogen or alkyl, especially hydrogen, and

n is a number from 1 to 10, with the proviso that n is not 1 when R is(meth)acryloyl, R² and R³ are methyl and R¹ and R⁴ are hydrogen.

Preferably R is an olefinically unsaturated acyl radical represented bythe formula ##STR6## where R⁵ is a C₂ to C₂₃ organic radical having apolymerizable olefinically unsaturated functionality.

Illustrative of olefinically unsaturated organic radicals R are thosehaving the formula: R⁵ --C(O)--, and more specifically the followingformula: ##STR7## wherein X is hydrogen or a C₁ -C₁₀ alkyl, carboxylicacid, ester, amide group or a nitrile,

Y is --O--, --CH₂ O--, --NR⁶ --, --CH₂ NR⁶ --, --(CO)--O--(CH₂)_(a)--NR⁶ --, where R⁶ is hydrogen or a C₁ -C₄ alkyl radical and a is 1 to4, --O(CO)--, --N(CO)--, a branched or unbranched C₁ to C₈ alkylenegroup, preferably polymethylene, or a substituted or unsubstitutedarylene group, especially phenylene,

Z is hydrogen, a C₁ -C₄ alkyl, ester, amide or carboxylic acid, or ahalogen or nitrile group, and

m is 0 or 1.

R can also represent a vinyl sulfonyl group.

Another example of olefinically unsaturated organic radical R whichcontains functionality that renders the nitrogen atom electron deficientis vinyl substituted melamine having the following formula: ##STR8##wherein R⁵ is as defined above and Q represents hydrogen, hydroxy, C₁-C₄ alkoxy or alkylamino or ##STR9##

Preferably, R represents a C₃ -C₂₄ alkenoyl radical such oleoyl,linoleoyl, and linolenoyl, particularly an alpha,beta-unsaturated C₃-C₁₀ alkenoyl group such as acryloyl, methacryloyl, crotonyl,isocrotonoyl, cinnamoyl, and the like, especially an acryloyl.

Thus the olefinic unsaturation can be incorporated into the monomer byorganic radicals [R--, or R--N--] of (meth)acrylamide; maleamides,including maleamic acid, maleamic acid ester, maleamide; fumarate;fumaramic acid; fumaramide; allyl or vinyl carbamate, urea, oxamide oroxamide-ester; vinyl benzamide, vinyl or allyl ether.

R¹ is preferably hydrogen but can be a C₁ -C₄ alkyl radical such asmethyl, ethyl or butyl. The hydrogen radical is preferred since itpermits acid catalyzed intracyclization when n is 2 to 5, preferably 3or 4, especially n=3, forming the respective cyclic hemiamidals.

In general formula I, R and R¹ together with the nitrogen atom can be a3-6 carbon containing α,β-unsaturated or alpha-methylene substitutedlactam.

R² and R³ represent hydrogen, C₁ -C₄ alkyl groups, such as methyl,ethyl, isopropyl and butyl, C₁ -C₄ acyl groups such as acetyl andpropionyl, or R² and R³ together may represent a C₂ -C₄ alkylene groupsuch as ethylene, propylene, or butylene. The alkyl groups arepreferred, especially methyl and ethyl.

The --(CH₂)_(n) -- group linking the nitrogen and the acetal or ketalfunctionality may also contain heteroatoms such as oxygen and nitrogen,for example, --CH₂ OCH₂ --, or other substituents on the carbon chain,for example, alkyl or aryl substituents.

Since the acetal and ketal compounds are preferred, R⁴ is preferablyhydrogen or a C₁ -C₄ alkyl group such as methyl, ethyl or butyl. Themonomer compounds of choice are the dialkyl acetals with R⁴ beinghydrogen.

The monomer compounds of the invention can be prepared by the well-knownaddition reaction of amines to acid chlorides in the presence of a baseto remove HCl according to the following general reaction: ##STR10##where R, R¹, R², R³, R⁴ and n are as defined above. For example, a2-phase reaction involving methylene chloride and aqueous sodiumhydroxide can be used. Merely illustrative of numerous acid chlorideswhich can be used for attaching the respective R group to the respectivenitrogen atom are the following: ##STR11## which are readily availablematerials or can be easily synthesized by well known preparativeprocedures.

Another reaction for the preparation of the monomer compounds is theaddition of aminoacetal compounds to maleic anhydride in an inertsolvent as illustrated by the following: ##STR12##

Still another route to the acetal and ketal monomers of the inventioncomprises reaction of an appropriate olefinically unsaturated carboxylicacid with an amino acetal or ketal using dehydrating agents such asSOCl₂ or carbodiimides. The direct reaction of acid and amine is alsoknown, but requires substantially higher temperatures.

In the reaction of an alkylamine with alkyl acrylates to giveacrylamides, the frequently observed faster Michael addition of theamine to the double bound produces both Michael addition and amideformation, but at higher temperatures the former reaction is reversible,allowing net formation of N-alkylacrylamides. The Michael reaction canalso be suppressed by pre-forming reversible alcohol- oralkylamine-acrylate adducts.

The transamination of olefinically unsaturated amides with theappropriate amino acetal or ketal salt at elevated temperatures isanother suggested preparative route. The synthesis of acrylamidesdirectly from primary and secondary amines, acetylene and carbonmonoxide is known and may prove useful here. The preparation ofacrylamides by the Pd catalyzed amidation of vinyl halides with aminesand carbon monoxide is also known.

The amino acetals or ketals can be prepared readily by standard organicchemistry synthetic procedures. For example: ##STR13## which is readilyavailable from hydroformylation of acrylonitrile in alcohol can behydrogenated to afford ##STR14##

Alternatively, acrolein or methyl vinyl ketone can be treated with HClin alcohol and then with sodium cyanide and the product hydrogenated.

The dialkyl acetal or ketal monomer of general formula I in which R¹ ishydrogen can be cyclized to a hemiamidal or a hemiamide ketal of theinvention represented by the general formula II by an acid catalyzedreaction. The reaction medium may be any typical organic solventincluding ketones such as acetone and methyl ethyl ketone, alcohols,methylene chloride and tetrahydrofuran. The reaction medium may containwater in amounts from 0 to 100%. Suitable acid catalysts for performingthe cyclization reaction include oxalic acid, p-toluenesulfonic acid,strong acid ion-exchange resins and mineral acids, e.g. HCl and H₂ SO₄.

Representative of the dialkyl acetal or ketal monomeric compounds of theinvention are the following:

acrylamidobutyraldehyde diethyl acetal (ABDA)

acrylamidobutyraldehyde dimethyl acetal (ABDA-Me)

acrylamidobutyraldehyde dipropyl acetal

acrylamidobutyraldehyde diisopropyl acetal

acrylamidobutyraldehyde dibutyl acetal

acrylamidobutyraldehyde methylethyl acetal

acrylamidobutyraldehyde diacetyl acetal

acrylamidopentanal diethyl acetal (APDA)

acrylamidopentanal dimethyl acetal

acrylamidopentanal dipropyl or diisopropyl acetal

acrylamidohexanal dimethyl acetal

acrylamidohexanal diethyl acetal

acrylamidohexanal dipropyl acetal

acrylamidoheptanal dimethyl acetal

acrylamidoheptanal diethyl acetal

acrylamidoheptanal dipropyl acetal

crotonamidobutyraldehyde dimethyl acetal

crotonamidobutyraldehyde diethyl acetal (CBDA)

crotonamidobutyraldehyde diisopropyl acetal

methacrylamidobutyraldehyde diethyl acetal

methacrylamidobutyraldehyde dimethyl acetal

methacrylamidobutyraldehyde diisopropyl acetal

(meth)acrylamidopropionaldehyde dimethyl acetal

(meth)acrylamidopropionaldehyde diethyl acetal

diethoxybutylmaleamic acid (DBMA)

diethoxybutylmaleamic acid methyl, ethyl or isopropyl ester

cinnamamidobutyraldehyde diethyl acetal (DEBC)

O-allyl-N-(diethoxybutyl)carbamate (ADBC)

O-allyl-N-(dimethoxypentyl)carbamate

O-vinyl-N-(diethoxybutyl)carbamate (DBVC)

O-vinyl-N-(dimethoxypentyl)carbamate

N-vinyl-N'-(dialkoxyethyl)urea or thiourea

N-vinyl-N'-(dialkoxybutyl)urea or thiourea

N-allyl-N'-(dialkoxyethyl)urea (ADEEU) or thiourea

N-allyl-N'-dialkoxybutylurea or thiourea

N-(diethoxybutyl)-N'-(meth)acryloxyethyl urea (DEBMU)

N-(dialkoxypropyl)-N'-(meth)acryloxyethyl urea

N-(diethoxyethyl)-N'-(meth)acryloxyethyl urea (DEEMU) or thiourea

N-allyl-O-dialkoxyethyl carbamate

N-vinyl-O-dialkoxyethylcarbamate

N-(diethoxybutyl)vinylsulfonamide

N-(diethoxybutyl)vinylphosphoramide

N-(diethoxybutyl)vinylbenzenesulfonamide

N-(diethoxybutyl)vinylaniline

N-(diethoxybutyl)vinylbenzylamine

O-(2,2-dialkoxy)propyl-N-(meth)acryloxyethylcarbamate

1-(meth)acrylamidohexan-5-one dialkyl ketal

1-(meth)acrylamido-4,4-dimethylhexan-5-one dialkyl ketal

2,2-dimethyl-5-(meth)acrylamidopentanal dialkyl acetal

Illustrative of the cyclic hemiamidals which can be prepared from theabove precursors in which a hydrogen atom is attached to the nitrogenatom, in other words R¹ in the general formula I represents hydrogen,are the following compounds:

N-acryloyl-2-ethoxypyrrolidine (AEP)

N-acryloyl-2-methoxypyrrolidine (AMP)

N-(meth)acryloyl-2-hydroxypyrrolidine (AHP)

2-N-(meth)acryloylpyrrolidine acetate

N-(meth)acryloyl-2-alkoxypiperidine

N-(meth)acryloyl-2-hydroxypiperidine

N-(meth)acryloyl-3-alkoxymorpholine

N-(allyloxycarbonyl)-2-alkoxypiperidine

N-(allyloxycarbonyl)-2-alkoxypyrrolidine

N-vinyloxycarbonyl-2-alkoxypyrrolidine

N-vinyloxycarbonyl-2-alkoxypiperidine

1-allyl-5-alkoxy-2-imidazolidone

1-allyl-5-alkoxy-2-imidazolidinethione

1-(meth)acryloxyethyl-5-alkoxy-2-imidazolidone

N[N'-(meth)acryloxyethyl]aminocarbonyl-2-alkoxypyrrolidine

1-allyl-6-ethoxy-(4-methyl)hexahydropyrimidin-2-one (AEMHP)

N-(meth)acryloyl-2-alkoxyperhydroazepine

N-(meth)acryloyl-2-alkoxyazetidine

N-crotonyl-2-alkoxypyrrolidine

N-cinnamoyl-2-alkoxypyrrolidine

N-vinylsulfono-2-alkoxypyrrolidine

N-allylsulfono-2-alkoxypyrrolidine

N-vinylphosphono-2-alkoxypyrrolidine

alkyl N-(but-2-en-1-on-3-carboxylate-1-yl)-2-alkoxypyrrolidine

N-allyl-4-alkoxyoxazolidin-2-one

N-vinylbenzenesulfono-2-alkoxypyrrolidine

N-(vinylphenyl)-2-alkoxypyrrolidine

N-(vinylbenzyl)-2-alkoxypyrrolidine

N-(meth)acryloxyethyl-5-alkoxy-5-methyl-2-imidazolidone

N-(meth)acryloxyethyl-4-alkoxy-4-methyloxazolidone

N-(meth)acryloyl-2-alkoxy-2-methylpyrrolidine

N-(meth)acryloyl-2-hydroxy-2,3,3-trimethylpiperidine

Alkyl N-allyl-5-alkoxypyrrolidone-5-carbonylate

N-[3-(alkoxycarbonyl)acryloyl]-2-alkoxypyrrolidine

The dialkyl acetal and ketal compounds and the cyclic hemiamidal andhemiamide ketal compounds of the invention being olefinicallyunsaturated can be homopolymerized, or polymerized in any amount, forexample, ranging from greater than 0 to over 99 wt %, with each otherand/or other copolymerizable monomers. It is preferred that thecopolymers contain about 0.5 to 10 wt % of the acetal, ketal and/orcyclic hemiamidal or hemiamide ketal monomers of the invention,especially about 1 to 3 wt % in nonwoven binder polymers.

Suitable copolymerizable monomers include monoolefinically andpolyolefinically unsaturated monomers including C₃ -C₁₀ alkenoic acids,such as acrylic, methacrylic, crotonic and isocrotonic acids and theiresters with C₁ -C₁₈ alkanols, such as methanol, ethanol, propanol,butanol and 2-ethylhexyl alcohol (C₄ -C₂₈ alkyl acrylates);alpha,beta-unsaturated C₄ -C₁₀ alkenedioic acids such as maleic acid,fumaric acid and itaconic acid and their monoesters and diesters withthe same C₁ -C₁₈ alkanols; vinyl halides such as vinyl chloride andvinyl fluoride; vinylidene halides such as vinylidene chloride; alkenes,such as ethylene, propylene and butadiene; styrene, vinyltoluene andother substituted styrenes; and nitrogen containing monoolefinicallyunsaturated monomers, particularly nitriles, amides, N-methylol amides,lower alkanoic acid esters of N-methylol amides, lower alkyl ethers ofN-methylol amides and allyl carbamates, such as acrylonitrile,acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methylol allyl carbamate and N-methylol lower alkylethers and N-methylol lower alkanoic acid esters ofN-methylolacrylamide, N-methylol methacrylamide and N-methylol allylcarbamate; vinyl esters of C₁ -C₁₈ alkanoic acids, such as vinylformate, vinyl propionate, vinyl laurate and especially vinyl acetate;vinyl ethers, such as methyl vinyl ether and isobutyl vinyl ether; andvinylamides such as N-vinyl pyrrolidone, N-vinylacetamide andN-vinylformamide.

The preferred polymers incorporating the cyclic and open chain monomersof the invention are prepared with 90 to 99.5 wt % of the followingcomonomer systems: vinyl acetate; vinyl acetate-ethylene; vinylchloride-ethylene; C₄ to C₂₈ alkyl acrylates such as butyl acrylate,methyl methacrylate and the like; vinyl acetate-acrylate; and styrene.In the vinyl acetate-ethylene and vinyl chloride-ethylene terpolymers,ethylene may compose 1 to 80 wt % of the polymer, preferably 5 to 40 wt%. In the vinyl acetate-acrylate terpolymers the acrylate may compose0.5 to 99 wt % of the polymer, preferably 15 to 50 wt %.

The cyclic hemiamidal and hemiamide ketal monomers and the dialkylacetal and ketal monomers can be homopolymerized, copolymerized witheach other or copolymerized with at least one of the abovecopolymerizable monomers by solution or aqueous emulsion polymerizationtechniques well known in the art. Such polymerization techniques aredescribed in such chemistry texts as Polymer Synthesis, Vol. I and II,by S. R. Sandler and W. Karo, Academic Press, New York and London(1974), and Preparative Methods of Polymer Chemistry, Second Edition, byW. R. Sorenson and T. W. Campbell, Interscience Publishers (John Wileyand Sons), New York (1968). Solvents which are suitable for solutionpolymerization include toluene, isopropanol, ethanol, methanol, benzene,acetone, ethyl acetate, acetonitrile, dimethylformamide, methyl ethylketone and water.

The monomers in the polymerization recipe can be added all at once ormetered into the polymerization reaction medium incrementally in anintermittent or continuous, preferably uniform, addition rate or anycombination thereof in order to take advantage of the variouspolymerization reactivities of the various monomers.

Catalytically effective amounts of various free-radical formingmaterials can be used in carrying out the polymerization of themonomers, such as peroxide compounds like peracetic acid, benzoylperoxide, and persulfate salt and azo compounds. Combination-typesystems employing both reducing agents and oxidizing agents can also beused, i.e. a redox system. Suitable reducing agents, or activatorsinclude bisulfites, sulfoxylates, or other compounds having reducingproperties such as ascorbic acid, erythorbic acid and other reducingsugars. The oxidizing agents include hydrogen peroxide, organicperoxides such as t-butyl hydroperoxide and the like, persulfates, suchas ammonium or potassium persulfate, and the like. Specific redoxsystems which can be used include hydrogen peroxide and zincformaldehyde sulfoxylate; t-butylhydroperoxide and erythorbic acid;hydrogen peroxide, ammonium persulfate, potassium persulfate or t-butylhydroperoxide with sodium metabisulfite, sodium bisulfite, ferroussulfate, zinc formaldehyde sulfoxylate, sodium formaldehyde sulfoxylateor sodium acetone bisulfite. Other free radical forming systems that arewell known in the art can also be used to polymerize the monomers.

The oxidizing agent is generally employed in an amount of 0.01 to 1%,preferably 0.05 to 0.5% based on the weight of the monomers introducedinto the polymerization system. The reducing agent is ordinarily addeddissolved in an appropriate solvent in the necessary equivalent amount.

With regard to aqueous emulsion polymerization techniques, again any ofthe well known emulsifying agents can be used, such emulsifying agentsinclude ionic and nonionic surfactants such as sodium lauryl sulfate,sodium sulfosuccinate esters and amides, sulfonated alkyl benzenes,alkylphenoxy polyethoxy ethanols and other polyoxyethylene condensates.

The concentration range of the total amount of emulsifying agents usefulis from less than 0.5 to 5% based on the aqueous phase of the emulsionregardless of a solids content.

Where necessary to maintain the pH of the aqueous emulsion reactionmedium, typical buffering systems can be employed.

In addition to or in place of the surfactants, protective colloids suchas polyvinyl alcohol and celluloses like hydroxyethyl cellulose, methylcellulose, hydroxypropyl methyl cellulose and the like can be used asthe emulsifying, or stabilizing, agent. When polyvinyl alcohol is addedup-front or during the polymerization reaction as the stabilizing agent,the monomers typically graft onto the polyvinyl alcohol backbone.

The cyclic hemiamidals and dialkyl acetal and ketal monomers of theinvention are a more general case of which normal amide/aldehyde adductsare a specialized example. Regarding the prior art technology, theproduct copolymers of N-methylolacrylamide (NMA), which is a condensateof acrylamide and formaldehyde, (1) crosslink efficiently under acidcatalysis via methylol or methylene coupling, (2) react well withsubstrates containing active hydrogen, e.g. cellulose and (3) are low incost. However, the formaldehyde is only weakly bound to the amide groupof NMA and both the initial and cured product can give off low butmeasurable levels of formaldehyde, a suspect as a cancer-causing agent.Substitution of other aldehydes or ketones usually exacerbates thisproblem, as their equilibria shift towards starting materials even morethan formaldehyde containing systems do.

The compounds of this invention circumvent this problem by attaching thealdehyde or ketone to the nitrogen (amide) portion of the molecule via acovalent chain. Especially when this chain is of an appropriate lengthto give a 5 or 6-membered ring with the nitrogen atom, the equilibriastrongly favor the cyclized material. With or without a favorableequilibrium, the aldehyde cannot be lost to the solution or theatmosphere. A practical example of this concept is shown. ##STR15##

Here the aldehyde is protected as its dialkyl acetal. As demonstrated bythe data and some model experiments described in the experimentalsection, these compounds interconvert under acid catalysis and canusually be used interchangeably in polymer and other applications.

To a first approximation, the cyclized form undergoes the sameself-crosslinking and coupling with active hydrogen containing compoundsas observed with NMA. Unlike NMA and other aldehyde based aminoplasts,both the dialkyl blocked aldehyde and ketone monomers and the cyclichemiamidal and hemiamideketal forms also contain a covalently boundblocked aldehyde or ketone which can react effectively with 1,2- and1,3-diols, such as ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-and 1,3-butylene glycol, 2,4-pentanediol and the like; a featureparticularly useful in reactions with polyvinyl alcohol which is 30 to100% hydrolyzed or cellulose and cellulose derivatives such as methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like;or for adhesion to metal oxide and other surfaces. Obviously, noformaldehyde is involved in the synthesis or decomposition of thesecompounds.

The reaction of the dialkyl acetal/ketal monomers and the cyclichemiamidal/hemiamide ketal monomers with active hydrogen-containingcompounds and substrates, such as the 1,2- and 1,3-diols, polyvinylalcohol, cellulose and metal oxide surfaces, can be catalyzed usingacidic materials such as mineral acids, like hydrogen chloride, ororganic acids, like oxalic acid or acid salts such as ammonium chlorideas is well known in the art of acetal and ketal formation and reaction.

The efficacy of these compounds in achieving lower energy cure thanstandard aminoplasts is not completely understood at this time. Thereactivity of these materials may simply be due to the fact that theintermediate N-acyliminium ion in the reaction from cyclohemiamidal tocrosslinked or substrate bound product is stabilized relative to theunsubstituted acyliminium species formed with formaldehyde basedaminoplasts. In the presence of 1,2- or 1,3-diols the thermodynamicallyfavored formation of cyclic acetals may provide a cure acceleratingmechanism.

Most previous attempts to solve this problem of formaldehyde liberationhave not used aminoplasts in which the aldehyde is bound via a covalentlinkage to the nitrogen atom, for example amide portion of theaminoplast molecule. This difference existing in the monomers of theinvention produces a number of beneficial results:

(a) the aldehyde cannot diffuse away from the amide portion of themolecule to produce toxic or irritating emissions, free radicalinhibition, or discoloration, as observed even with the electrondeficient aldehydes or formaldehyde used in prior art technology.

(b) the presence of bound and blocked aldehyde functionality allowsefficacious reaction with 1,2- and 1,3-diols to give particularlythermodynamically stable acetal formation, an additional crosslinkingmode not available to prior art systems; and

(c) use of a substituted hemiamidal often produces faster reaction thanobserved with other species.

Contemplated as the functional equivalent of 1,2- and 1,3-diols for thepurpose of this invention are 1,2- and 1,3-amine alcohols and diamines.

In addition, the ability to prepare enamides through loss of HOR² fromcyclic hemiamidals may prove important in crosslinking applications.

The dialkyl acetal/ketal and cyclic hemiamidal/hemiamide ketal monomersof the invention and their derived polymers are suitable for use ascrosslinkers and adhesion promoting agents in paints and other coatings,adhesives for glass, wood, paper, metal, ceramics and other substrates;formaldehyde free binders for nonwoven products, medical/surgicalapplications, diaper cover stock, wipes, towels, apparel, carpeting,fabrics, filtration products and home furnishings. They may also beuseful as co-reagents to reduce formaldehyde and/or improve adhesion andother performance factors when used with standard aminoplasts andphenoplasts.

The polymers derived from the dialkyl acetal/ketal monomers and cyclichemiamidal/hemiamide ketal monomers of the invention are useful asbinder compositions in the preparation of nonwoven products, or fabrics,by a variety of methods known to the art which, in general, involve theimpregnation of a loosely assembled mass of fibers with the copolymerbinder emulsion, followed by moderate heating to dry the mass. Thismoderate heating also usually serves to cure the binder by forming acrosslinked interpolymer. Before the binder is applied it is, of course,mixed with a suitable catalyst for the crosslinking monomer. Forexample, an acid catalyst such as mineral acids, e.g. hydrogen chloride,or organic acids, e.g. p-toluenesulfonic acid, or acid salts such asammonium chloride, are suitably used as is known in the art. The amountof catalyst is generally about 0.5 to 2% of the total resin. It has beendiscovered with respect to the binder polymers prepared using themonomers of the invention that simple amine acid salts, such as ammoniumchloride, ammonium acetate and methyl ammonium chloride are surprisinglythe preferred catalysts for crosslinking.

The starting fiber layer or mass can be formed by any one of theconventional techniques for depositing or arranging fibers in a web orlayer. These techniques include carding, garnetting, air-laying and thelike. Individual webs or thin layers formed by one or more of thesetechniques can also be laminated to provide a thicker layer forconversion into a fabric. Typically, the fibers extend in a plurality ofdiverse directions in general alignment with the major plane of thefabric, overlapping, intersecting and supporting one another to form anopen, porous structure.

When reference is made to "cellulose" fibers, those fibers containingpredominantly C₆ H₁₀ O₅ groupings are meant. Thus, examples of thefibers to be used in the starting layer are the natural cellulose fiberssuch as wood pulp, cotton and hemp and the synthetic cellulose fiberssuch as rayon, and regenerated cellulose. Often the fiber starting layercontains at least 50% cellulose fibers whether they be natural orsynthetic, or a combination thereof. Often the fibers in the startinglayer may comprise the natural fibers such as wool, jute; artificialfibers such as cellulose acetate; synthetic fibers such as celluloseacetate, polyvinyl alcohol, polyamides, nylon, polyester, acrylics,polyolefins, i.e. polyethylene, polyvinyl chloride, polyurethane, andthe like, alone or in combination with one another.

The fiber starting layer is subjected to at least one of the severaltypes of bonding operations to anchor the individual fibers together toform a self-sustaining web. Some of the better known methods of bondingare overall impregnation, or printing the web with intermittent orcontinuous straight or wavy lines or areas of binder extending generallytransversely or diagonally across the web and additionally, if desired,along the web.

The amount of binder, calculated on a dry basis, applied to the fibrousstarting web is that amount which is at least sufficient to bind thefibers together to form a self-sustaining web and suitably ranges fromabout 3 to about 100% or more by weight of the starting web, preferablyfrom about 10 to about 50 wt % of the starting web. The impregnated webis then dried and cured. Thus the fabric is suitably dried by passing itthrough an air oven or the like and then through a curing oven. Typicallaboratory conditions to achieve optimal cross-linking are sufficienttime and temperature such as drying at 150°-200° F. (66°-93° C.) for 4to 6 minutes, followed by curing at 300°-310° F. (149°-154° C.) for 3 to5 minutes or more. However, other time-temperature relationships can beemployed as is well known in the art, shorter times at highertemperatures or longer times at lower temperatures being used.

The monomers of the invention may also be useful as reactive diluents incoating compositions in which the aldehyde/cyclic hemiamidal moietyreacts first and the double bonds are reacted later by free radical ornucleophilic attack.

In addition, the compounds may be useful for modifying orfunctionalizing polyvinyl alcohol, cellulosics (wood, paper, rayon,cotton), starch or sugars through formation of cyclic acetals with 1,2-or 1,3-diols.

The following examples are illustrative of the invention and are notintended to limit the scope thereof.

EXAMPLE 1 Synthesis of Acrylamidobutyraldehyde Diethyl Acetal (ABDA)

4-Aminobutyraldehyde diethyl acetal (AmBDA, 75 g, 1.09 mol, AldrichChemical) was combined with a two phase mixture of 955 mL of CH₂ Cl₂ and160 mL of 14N NaOH in a 3 neck flask equipped with a thermometer and anefficient mechanical stirrer. This was cooled to 15° C. with an icebath. Acryloyl chloride (98.3 g, 1.09 mol, Aldrich) was added via anaddition funnel at a rate slow enough to maintain the reactiontemperature below 30° C. Reaction monitoring by capillary glpc revealedessentially complete AmBDA consumption when the acryloyl chlorideaddition was complete. Agitation was continued for 1 h. The layers wereseparated (water may be added to dissolve precipitated salt and improvephase separation) and the organic phase was washed with saturated brine.The brine was combined with the aqueous layer and back extracted withCH₂ Cl₂. The combined organic layers were neutralized with saturatedaqueous NaH₂ PO₄, dried over anhydrous MgCl₂ and concentrated on arotary evaporator at 40° C. to give 99% pure ABDA (by glpc) in 87%yield. The product can be freed of any high molecular weight by-productsby kugelrohr distillation (120°-125° C. at 0.2 torr), but this producessignificant yield losses and partial isomerization toN-acryloyl-5-ethoxy pyrrolidine (AEP) and related products. The pottemperature should not exceed 60° C. during these operations. The yieldloses are minimized by adding a basic reagent, such as Na₂ CO₃, and aradical inhibitor, such as methylene blue, to the distillation vessel.

IR(film): 3260, 1655, 1630, 1540 cm⁻¹

¹ H NMR (CDCl₃): δ6.25 (dd, 1, J=16.8, J=2.0 Hz, vinyl), 6.13 (v br, 1,NH), 6.10 (dd, 1, J=16.8, J=9.6 Hz, vinyl), 5.60 (dd, 1, J=9.6, J=2.0Hz, vinyl), 4.48 (br t, 1, J˜4.6 Hz, CH), 3.75-3.4 (m, 4, OCH₂), 3.32(br q, 2, J˜6.1 Hz, NCH₂), 1.65 (m, 4, CH₂ CH₂), and 1.20 (t, 6, J=6.9Hz, CH₃). The vinyl region changes on dilution or in other solvents. ¹³C NMR: δ125.65 (t), 131.38 (d), 165.93 (s), 39.36 (t), 24.65 (t), 31.32(t), 102.78 (d), 61.43 (t, 2C), 15.37 (t, 2C). MS: m/e 47, 55, 70, 75,103, 123, 124, 169, 170, 186, 214 (CI: M⁺ =215)

Anal. Calc'd for C₁₁ H₂₂ NO₃ : C, 61.37; H, 9.83; N, 6.51. Found: C,61.24; H, 9.87; N, 6.44.

EXAMPLE 2 Direct Synthesis of N-acryloyl-5-ethoxy pyrrolidine (AEP)

AmBDA (125 g, 0.78 mol) was mixed as above with 835 mL of CH₂ Cl₂ and124 mL of 14N NaOH. After cooling the mixture to 18° C., acryloylchloride (70 g, 0.78 mol) was added with efficient stirring to maintainthe reaction temperature below 30° C. (approximately one h). Shortlyafter acid chloride addition was completed, the AmBDA was observed byglpc to be consumed, producing 97% pure ABDA. Without an additionalreaction period, the combined layers were neutralized to pH 7.4 withconcentrated H₂ SO₄ and separated. The organic layer was dried withMgSO₄ and an aliquot was extracted with H₂ O to give a pH of 4.2,indicating hydrolysis or reaction of a low residual level of acryloylchloride to generate HCl. The organic layer was again neutralized (to pH7.2) with alcoholic KOH and concentrated on a rotary evaporator to yield108 g of light yellow liquid, 89% AEP (83.4% yield) and 2% ABDA. MEHQ(1000 ppm) was added as an inhibitor.

EXAMPLE 3 Synthesis of AEP from ABDA

A 40 g sample of ABDA analyzing as 70.1% ABDA and 23.9% AEP was mixedwith 400 mL of 3:1 CH₂ Cl₂ /EtOH and 10 g of strong acid macroreticularion exchange resin (Rohm and Haas XN-1010). The mixture was stirred atroom temperature and analyzed hourly by capillary glpc. Peak ratios were83.2% AEP and 11.1% ABDA after 1 h, and 87.0% AEP, 7.8% ABDA after 2 hand at 3 h. The resin was filtered off and the solvent removed.Kugelrohr distillation after neutralization (pH 6.4 with KOH/EtOH) gave28.7 g of product (90°-96° C., 0.15 torr) containing 92% AEP (77.5%yield based on ABDA conversion).

IR (film): 1645, 1610, 1445 cm⁻¹.

¹ H NMR (D₂ O): δ 6.45 (8 peak m, overlapping dd's, 1, J=10.4, J=16.8Hz, vinyl), 6.12 (overlapping dd's, 1, J=16.8, J˜1.6 Hz, vinyl), 5.70(overlapping dd's, 1, J˜10, J˜1.6 Hz, vinyl), 5.33 (d, ˜0.3, J=4.8 Hz,CH) +5.21 (d, ˜0.6, J=4 Hz, CH), 3.45 (m, 3, OCH₂), 2.19 (m, 1), 2.1-1.4(m, 4, CH₂ CH₂), 1.03 (overlapping t's, 3, J=6.5 Hz, CH₃). M/S: 41, 55,70, 86, 96, 112, 124, 125, 140 (CI (NH₃): M⁺ =169)

EXAMPLE 4 Synthesis of Acrylamidoacetaldehyde Dimethyl Acetal (AADMA)

To 125 g (1.19 mol) of aminoacetaldehyde dimethyl acetal in a rapidlystirred two phase mixture of 390 mL of methyl t-butyl ether (MTBE) and125 mL of 14N aqueous NaOH at 18° C. was added 107.5 g (1.19 mol) ofacryloyl chloride over 1 h (reaction temperature maintained below 30°C.). A precipitate (NaCl) separated out. After 15 min the pH wasadjusted to 7.1-7.8 (dil. NaOH) and the layers were separated. Theproduct was extracted into H₂ O (hexane added to the MTBE to drive theequilibrium). GC analysis showed 181 g AADMA in 700 mL of aqueoussolution, plus 10 g AADMA in the brine layer (100% yield).

EXAMPLE 5 Synthesis of AADMA with Product Isolation

Example 4 was repeated with 20 g of aminoacetaldehyde dimethyl acetal(0.19 mol), 17.2 g (0.19 mol) of acryloyl chloride, 125 mL of MTBE and20 mL of 14N NaOH. The separated organic layer was washed with brine.Additional aqueous extraction of the organic layer produced significantproduct loss to the aqueous phase. The aqueous layer was back-extractedtwo times with Et₂ O. The combined organic layers were dried withanhydrous MgSO₄ and concentrated on a rotary evaporator to give 25.5 gof light yellow liquid analyzing as 95% AADMA (84%). Cu bronze, 1000ppm, was added to this product and the mixture was subjected tokugelrohr distillation (105° C., 0.11 torr) to give 4 g of colorlessdistillate before the remainder resinified. The distilled product beganto resinify after several days in a freezer despite the addition of MEHQInhibitor (1000 ppm).

IR (film): 3290 (br), 1660, 1624, 1610 (sh), 1545 cm⁻¹.

¹ H NMR (CDCl₃): δ 6.3 (dd, 1, J=16.5, J=1.9 Hz, vinyl), 6.2 (dd, 1,J=16.5, J=9.6 Hz, vinyl+buried NH), 5.65 (dd, 1, J=9.6, J=1.9 Hz,vinyl), 4.43 (br t, 1, CH), 3.48 (apparent t, 2, NCH₂), 3.4 (S, 6, CH₃).

EXAMPLE 6 Synthesis of N-(2,2-Dimethoxyethyl)maleamic acid (DMEMA)

Aminoacetaldehyde dimethyl acetal (90 g, 0.857 mol) was added over 45min to a 16° C. mixture of 84 g (0.857 mol) of purified maleic anhydride(azeotropic removal of H₂ O by distillation of xylene from crudeanhydride) in 855 mL of CH₂ Cl₂ (reaction temperature below 30° C.).After 1 h all of the amine had reacted and the solvent was removed on arotary evaporator to yield a yellow solid. Recrystallization from MeOHgave 138 g (75% yield) of white solid, mp 91°-92° C. Furtherrecrystallization (toluene/MeOH) gave mp 93°-94.5° C.

IR: 3280, 1710, 1630, 1600, 1540 cm⁻¹.

¹ H NMR (CDCl₃): δ7.19 (br s, 1, NH), 6.38 (s, 2, vinyl), 4.49 (t, 1,J=5.0 Hz, CH), 3.55 (2d, 2, J˜5 Hz, CH₂) 3.41 (s, 6, CH₃); (CD₂ Cl₂):δ15.68 (s, 1, CO₂ H), 6.30, 6.31 (d's, 2, J=12.2 Hz, vinyl), 6.76 (1,NH), 4.49 (t, 1, J=4.9 Hz, CH), 3.56 (2d, 2, J=4.9 Hz), 3.40 (s, 6,CH₃).

EXAMPLE 7 Synthesis of O-Allyl-N-(4,4-diethoxybutyl)carbamate (ADBC)

1) Two Phase

To 3.22 g (2.0 mmol) of 4-aminobutyraldehyde diethyl acetal in a twophase rapidly stirred mixture of 20 mL of CH₂ Cl₂ and 20 mL of 2N NaOHat 0° C. was added 2.41 g (2.0 mmol) of allyl chloroformate (temperaturemaintained below 30° C.). The layers were separated and the organiclayer was washed with H₂ O and dried over 3A molecular sieves. Thesolution was concentrated on a rotary evaporator to yield a light yellowliquid.

2) Single Phase

Ethanol (50 ml) was cooled to 0° C. and treated with 2.41 g ofallylchloroformate and 3.22 g of aminobutyraldehyde diethyl acetal.After 20 min the pH was 1.8, after 35 min it was 1.2. The sample wasneutralized slowly with triethylamine (22.4 mL to a stable pH of 7.3 (1hr.)). The mixture was concentrated at 50° C., diluted with CH₂ Cl₂ andreconcentrated. On Et₂ O dilution, a white precipitate of Et₃ NHCl (mp256° C.) separated. The Et₂ O solution was washed (H₂ O and brine) andfiltered through 3A molecular sieving zeolite. Concentration yielded3.42 g of yellow liquid.

IR (film): 3320 (NH), 1700 (carbamate), 1650 (vinyl), 1520 (NH), 1060cm⁻¹ ; ¹ H NMR (CDCl₃): δ 5.91 (m, 1, J˜5.6 Hz, vinyl), 5.28 (dd, 1,J=16.6, J˜1.6, vinyl), 5.20 (dt (?), 1, J=10.3, vinyl), 5.05 (br, 1,NH), 4.58 (br t, 2, J˜5 Hz, allyl), 4.49 (t?, 1, J˜4.7 Hz, CH), 3.58 (m,4, OCH₂), 3.2 (q, ˜2, J˜5.6 Hz, NCH₂), 1.6₃ (m, 4, CH₂ CH₂), 1.2 (t, 6,J=6.8 Hz, CH₃).

EXAMPLE 8 O-Allyl Carbamate of 2-Ethoxypyrrolidine by the Isomerizationof ADBC

ADBC (2 g) was added to 20 mL of CH₂ Cl₂ and anhydrous HCl was bubbledthrough the mixture for 5 min. The solution was heated to 38° C. for 1.5h. The sample was washed with H₂ O and the aqueous phase wasback-extracted with CH₂ Cl₂. The combined organics were dried with MgSO₄and concentrated to yield 1.33 g of yellow liquid. This sample (0.75 g)was submitted to preparative thin layer chromatography on silica gel(3:1 Et₂ O/hexane) to yield 5 spots by UV:rf 0.58 (30 mg), 0.49 (145mg), 0.41 (135 mg), 0.26 (129 mg), origin (26 mg). The remainder alsogave 107 mg of mixed fractions. The second and third fractions werelargely the desired O-allyl carbamate of 2-ethoxypyrrolidine:

IR: no NH, 1700, 1650 (sh), 1400 cm⁻¹.

¹ H NMR (CDCl₃): δ5.95 (m, 1, vinyl), 5.4-5.25 (m, 3, vinyl+NCHO), 4.63(d, 2, allyl), 3.75-3.3 (m, 4, OCH₂ +NCH₂), 2.2-1.65 (m, 4, CH₂ CH₂),1.2 (t, 3, CH₃).

The remaining fractions were largely the O-allyl carbamate of 2-hydroxypyrrolidine:

IR (film): 3420, 1690, 1650 (sh), 1400 cm⁻¹.

¹ H NMR (CDCl₃): δ 5.95 (m, 1, vinyl), 5.43 (br d, 1, vinyl), 5.2 (m,˜2, vinyl+NCHO), 4.6 (br d, 2, allyl), 3.7-3.1 (m, 2, NCH₂), 2.1-1.5 (m,4, CH₂ CH₂).

EXAMPLE 9 Synthesis of N-(4,4-Diethoxybutyl)maleamic Acid (DBMA)

Maleic anhydride (85 g) in 1300 mL of CH₂ Cl₂ was cooled to 15° C. andtreated with 155 g of 4-aminobutyraldehyde diethyl acetal (AmBDA).(Other preparations used the reverse mode of addition with similarresults.) Fifteen min after the addition was complete no further AmBDAwas detected by glpc. The solvent was removed under reduced pressure(maintained at 0.2 torr for 2 h to assure completion) to give 230 g ofslightly orange colored thick oil. On standing for several months at 0°C., this material solidified to an off-white solid.

IR (film): 3260 (NH), 1700 (amide), 1630, 1550 cm⁻¹.

¹ H NMR (CD₂ Cl₂): δ˜14 (v br, ˜1, CO₂ H), 8.83 (br t, 1, NH), 6.43 (d,1, J=13.3 Hz, vinyl), 6.25 (d, 1, J=13.3 Hz, vinyl), 4.47 (br t, 1, CH),3.7-3.4 (m, 4, OCH₂), 3.34 (m, 2, NCH₂), 1.63 (br s, 4, CH₂ CH₂), 1.20(t, 6, J=6.8 Hz, CH₃).

EXAMPLE 10 Synthesis of 4-Acetamidobutyraldehyde Diethyl Acetal

This reaction followed the procedure of Example 1, but using 50 g (0.31mol) of AmBDA, 24.3 g (0.31 mol) of acetyl chloride, 330 mL of CH₂ Cl₂and 50 mL of 14N NaOH. Thirty min after the acid chloride addition wascompleted the reaction was adjusted to pH 7.7 with 30% H₂ SO₄ and solidCO₂ was added to give a pH of 6.4. The separated aqueous layer wasextracted with CH₂ Cl₂ and the combined organic layers were washed withbrine, dried with anhydrous MgSO₄ and concentrated to give 69 g of paleyellow liquid. This sample plus 1000 ppm of MEHQ and 0.6 g of copperbronze were distilled on a kugelrohr apparatus (120° C., 0.02 torr) togive 45 g of colorless oil (65% yield).

IR: (film) 3290, 1650, 1555, 1440 cm⁻¹.

¹ H NMR (CDCl₃): δ 6.40 (br s, 1, NH), 4.64 (t, imp. or CH rotamer),4.47 (t, ˜1, J=5 Hz, CH), 3.4-3.75 (m, 4, OCH₂), 3.23 (q, 2, J=6.5 Hz,NCH₂), 2.62 (m, 4, CH₂ CH₂), 1.96 (s, 3, CH₃), 1.20 (t, 6, J=7.2 Hz,CH₃).

EXAMPLE 11 Synthesis of 4-(Aminoethyl)butyraldehyde Diethyl Acetal

Acetamidobutyraldehyde diethyl acetal (25 g, 0.123 mol) was slowly addedto 4.7 g (0.123 mol) of lithium tetrahydridoaluminum in 150 mL of dryTHF at reflux. After 1 h the excess LiAlH₄ was destroyed by adding EtOAcand the reaction was treated with 1-2 mL of saturated aqueous Na₂ SO₄.The green gelatinous mixture was vacuum filtered and the organic phasewas concentrated on a rotary evaporator. The inorganic phase wasextracted with EtOAc and again with THF and the combined concentratedorganic phases were distilled on a kugelrohr apparatus (105°-130° C. at0.2 torr) to yield 9.26 g of yellow liquid. Capillary gc analysis andnmr revealed the mixture to be 75% 4-(aminoethyl)butyraldehyde diethylacetal (30% yield).

IR: (film) 1745 (v.w., imp), 1655 (w), 1450, 1126, 1063 cm⁻¹.

¹ H NMR (CDCl₃): δ 5.66 (t, imp?), 5.51 (Tt ˜1, J=5 Hz, CH), 3.4-3.75(m, 4, OCH₂), 2.7-2.3 (m, ˜4, CH₂ NCH₂), 1.61 (m, ˜4, CH₂ CH₂), 1.21 (t,J=3.5 Hz), 1.11 (t, J=3.5 Hz)+1.02 (t, J=3.5 Hz) last three in 62:17:20ratio, rotamer mix.

EXAMPLE 12 Synthesis of N-Ethylacrylamidobutyraldehyde Diethyl Acetal(Et-ABDA)

4-(Aminoethyl)butyraldehyde diethyl acetal (8.5 g, 0.045 mol) in 56 mLof CH₂ Cl₂ was rapidly stirred with 8 mL of 14N NaOH at 20° C. Acryloylchloride (3 g, 0.045 mol) was added slowly to maintain the temperaturebelow 30° C. GC analysis at 30 min showed no remaining starting materialand a new product at 8.65 min. The mixture was neutralized with 30% H₂SO₄ and buffered with solid CO₂. The organic phase was concentrated anddistilled (kugelrohr) to give 6.5 g of yellow liquid (100°-125° C., 0.15torr). GC analysis showed 82% of the 8.65 min peak (53% yield) plus 4minor components.

¹ H NMR (CDCl₃): δ 6.56 (dd, <1, J=10.3 Hz, J=16.2 Hz, vinyl), 6.32 (dd,<1, J=16.2 Hz, J=2.0 Hz, vinyl), 5.65 (dd, <1, J=10.3 Hz, J=2.0 Hz,vinyl), 4.47 (br t, 1, methine), 3.8-3.2 (m, ˜8, NCH₂, OCH₂), 1.65 (m,4, (CH₂)₂), 1.20 (t, 9, J=6.7 Hz, CH₃).

EXAMPLE 13 Reactions of N-Acetyl-4-aminobutyraldehyde Diethyl Acetal

1) In MeOH.

N-Acetyl-4-aminobutyraldehyde diethyl acetal (A) (15 g) was added to 185mL of 3:1 CH₂ Cl₂ /MeOH. Rohm and Haas XN-1010 strong acidmacroreticular ion exchange resin (4 g) was added and the mixture wasstirred slowly at ambient temperature. After 15 minute, analysis by glpcshowed additional components at shorter retention times than A. At 1.5 hthe XN-1010 was filtered off and the solution was concentrated to give13.8 g of light yellow liquid analyzing as 70%N-acetyl-2-methoxy-pyrrolidine (E, retention time 5.66 min), 6.4%N-acetyl-2-ethoxy-pyrrolidine (D, r.t. 5.99 min), 17.3%N-acetyl-4-aminobutyraldehyde dimethylacetal (C, r.t.=7.05 min), 3%N-acetyl-4-aminobutyraldehyde ethyl methyl acetal (B, r.t.=7.34 min),and 1.6% N-acetyl-2-pyrroline (G, r.t.=4.74 min).

E, 'H NMR (CDCl₃): δ5.43 (d, 0.4, J=4.6 Hz, NCHO)+4.96 (d, 0.6, J=4 Hz,NCHO), 3.48+3.39 (s's, 3, CH₃), 3.8-3.3 (m, NCH₂ +OCH₂ CH₃ imp?), 3.30(s, MeOH?), 2.16+2.09 (s's, 3, CH₃), 2.2-1.6 (m, 4, CH₂ CH₂). Thissample contains signals attributable to the ethyl acetal and ethanol byglpc. GC/MS: m/e 43, 70, 100, 113, 143 (confirmed by NH₃ -CI).

D: GC/MS m/e 43, 70, 85, 86, 113, 128, 142, (M⁺ =157 by CI).

C: GC/MS, m/e 43, 70, 75, 85, 100, 128, 144, 160 (M⁺ =175 by CI).

B: GC/MS, m/e 43, 61, 70, 85, 89, 100, 114, 144, 158, 174 (M⁺ =189 byCI).

A: GC/MS, m/e 43, 47, 70, 75, 103, 114, 158, 174, 202 (M⁺ =203 by CI).

G: GC/MS, m/e 43, 68, 69, 111 (M⁺ =112 by CI).

2) In CH₂ Cl₂ :

To 1 g of A (7477-38) in 12 mL of CH₂ Cl₂ was add 0.27 g of XN-1010. Themixture was stirred at room temperature. After 1.5 h less than 1% Aremained with D as the major product (88%) by glpc. Minor amounts ofN-acetyl-2-hydroxypyrrolidone (F), a broad peak at r.t. ˜5.6 min (1.9area %) and N-acetyl-2-pyrroline (G), r.t. ˜4.74 min (9.6%) were alsoformed.

F: GC/MA; m/e 43, 59, 68, 70, 72, 86, 101, 111, 114, 129 (NH₃ CI: 70,77, 112, 129, 145)

3) Back Isomerization of N-Acetyl-2-methoxypyrrolidine (E).

Six mL of the product of 2) above was diluted with 2 mL of MeOH andcatalyzed with 0.13 g of XN-1010. After 1 h at room temperature Edecreased from 90.8 to 77.2% and C (acetamidobutyraldehyde dimethylacetal) increased from less than 1% to 4.9%. The other major product wasG (14.2%).

4) Reaction of N-Acetyl-4-aminobutyraldehyde diethyl acetal (A) with2,4-Pentandiol.

One g of A and 0.51 g of 2,4-pentandiol (epimeric mix) were heated in 1g of H₂ O with p-toluenesulfonic acid (10 mg at 50° C./1 h, then anadditional 10 mg at 70° C. for 2.5 h). An aliquot was neutralized withKOH/EtOH, extracted with H₂ O and CH₂ Cl₂ (2× each), back extracted withbrine and concentrated. Glpc analysis showed two major product peaks(8.34 and 8.71 min). The 'H NMR was consistent with a mixture ofepimeric cyclic 2,4-pentandiol acetals of A.

'H NMR (CDCl₃): δ6.11 (br s, 1, NH), 4.86 (low t) 4.56 (br t, ˜1, CHO₂),4.3-3.85 (series of m, ˜1), 3.71 (m, ˜2, CHO), 3.48 (q, imp.), 3.24 (m,2+, NCH₂), 1.96 (s, 3, CH₃), 1.7-1.3 (m, ˜6, CH₂), 1.21 (m, 6+imp.,CH₃).

5) Reaction of N-Acetyl-2-methoxypyrrolidine (E) with 2,4-Pentandiol.

One g of N-acetyl-2-methoxypyrrolidine (largely E plus lesser an amountsof B, C and D), 0.9 g of 2,4-pentandiol and 240 mg ofN-methyl-2-pyrrolidone internal standard were heated at 50°-55° C. in 1mL of H₂ O. A separate sample was heated in 1 mL of EtOAc. Results inboth samples were similar: rapid initial formation of a small peak at8.02 min (cyclic hemiamidal of the diol?), followed by growth of majorproduct peaks at 8.35 and 8.73 min, the epimeric cyclic acetals. Smallquantities of dehydrated product G (r.t.=4.75 min), and, in the aqueoussample, N-acetyl-2-hydroxypyrrolidine, F (before A at ˜5.6 min) werealso produced. One of the diols appeared to react faster and to agreater extent than the other. Measurements at 3-4 hr were close to theovernight values: ˜87% conversion of A, 60-70% of B and essentiallyquantitative conversion of C and D.

EXAMPLE 14 Additional AEP Derivatives

Three analogs of N-acryloyl-5-ethoxy pyrrolidine (AEP) were preparedsimilarly to Examples 2 and 3 using the appropriate alcohol or wateraccording to the following reaction scheme: ##STR16## AHP (R=H)N-acryloyl-5-hydroxypyrrolidine AMP (R=Me)N-acryloyl-5-methoxypyrrolidine

AiPP (R=iPr) N-acryloyl-5-i-propoxypyrrolidine

EXAMPLE 15

The following additional dialkyl acetal monomers were prepared:

a) N-(2,2-diethoxyethyl)-N'-(2-methacryloxy)ethyl urea (DEEMU) DEEMU isan example of a methacrylate moiety and a heteroatom in the organiccarbonyl radical which radical renders the nitrogen atom electrondeficient.

A mixture of 50 mL of CH₂ Cl₂ and 13.3 g (0.1 mol) of aminoacetaldehydediethyl acetal was cooled to 10°-15° and 14.1 g (0.095 mol) ofisocyanatoethyl methacrylate (ICEM) was added at a rate to maintain thereaction below 30° C. Stirring was continued for 1 h. Since some ICEMremained, 2 mL of H₂ O and small amounts of MeOH and stannous octoatewere added. The solution was washed two times with 10 mL of brine, mixedwith 40 mL of MeOH, dried over MgSO₄ and concentrated on a rotaryevaporator. The yellow oil, 17 g (62% yield) partially decomposed on gcanalysis, but gave the expected nmr.

nmr(CD₂ Cl₂): δ 1.2(t, 6, CH₃), 1.9(s, 3, CH₃), 3.2(t, 2, CH₂ N),3.3-3.8(m, 6, OCH₂, NCH₂), 4.2(t, 2, CH₂ O), 4.5(t, 1, CH), 4.9(br.s, 1,NH), 5.1(brs, 1, NH), 5.6(m, 1, vinyl), and 6.1 ppm(m, 1, vinyl).

b) N-(4,4-diethoxybutyl)-N'-methacryloxyethyl urea (DEBMU) DEBMU isanother example of a monomer of the invention incorporating amethacrylate moiety as part of the olefinically unsaturated radical thatrenders the nitrogen atom electron deficient.

To 100 mL of CH₂ Cl₂ and 32.2 g (0.2 mole) of 4-aminobutyraldehydediethyl acetal cooled to 10°-15° C. was added 29.6 g (0.19 mol) ofisocyanatoethyl methacrylate at a rate slow enough to maintain thetemperature below 30° C. The solution was stirred an additional 1 h,then washed two times with 10 mL of brine, diluted with 50 mL of MeOH,dried over anhydrous MgSO₄ and concentrated on a rotary evaporator. Theproduct (60 g, 99% yield) was stabilized with MEHQ. This productdegraded significantly on attempted gc analysis (major peak at 10 minrt).

nmr(CD₂ Cl₂): δ 1.2(t, 6, CH₃) 1.3-1.8(m, 4, CH₂ CH₂), 1.9(d, 3, CH₃),3.2(q, 2, CH₂ N), 3.3-3.7(m, 6, CH₂ N, CH₂ O), 4.2(t, 2, CH₂ O), 4.4(t,1, CH), 5.0(br.t, 1, NH), 5.1(br.t, 1, NH), 5.6(m, 1, vinyl), 6.1 ppm(m, 1, vinyl).

c) Acrylamidopentanaldehyde diethyl acetal (APDA) APDA illustrates thenext higher analog of ABDA.

i) Synthesis of Cyanobutyraldehyde Diethyl Acetal. A mixture of 50 g(0.51 mol) of 4-cyanobutyraldehyde, 100 mL of heptane, 100 mL ofabsolute EtOH and 1 g of Rohm and Haas XN-1010 strong acidmacroreticular cation exchange resin where heated and the water-heptaneazeotrope was separated in a Dean Stark trap. No further H₂ O distilledover after 49 mL of H₂ O had collected. The trap was replaced with asoxhlet extractor containing 3A molecular sieving zeolites, and heatingwas continued for 3 h. The supernatant was concentrated over solid Na₂CO₃ and distilled on a kugelrohr apparatus from solid Na₂ CO₃ (90° C.bath, 0.05 torr). The product (68 g, 78.4% yield) was 97% of a singlecomponent by gc (r.t. 5.24 min).

nmr (CD₂ Cl₂): δ 1.16(t, 6, J=7.0 Hz, CH₃), 1.7(m, 4, CH₂ CH₂), 2.3 (m,2, NCCH₂), 3.4-3.7(m, 4, CH₂) and 4.45 ppm (m, 1, CH).

ir (film): 2250, 1130, 1070 cm⁻¹.

ii) Synthesis of 5-Aminopentanal Diethyl Acetal. A 500 mL Paar shakerbottle was charged with 48 g of cyanobutyraldehyde diethyl acetal (0.28mol), 250 mL of EtOH (saturated with NH₃) and approximately 15 g ofactive W. R. Grace Raney nickel catalyst. The system was purged 2 timeswith N₂ and 3 times with H₂. The shaker was turned on and reactioninitiated at 50 psia and room temperature using a 4 L H₂ reservoir whichwas repressurized twice over 6 h. Approximately 0.66 mol H₂ wasconsumed. The product was filtered, concentrated (41 g) and distilled(92° C., 10 torr) to yield a material with essentially the same gcretention time as the starting material (5.03 min), but no nitrile byir.

nmr (CD₂ Cl₂): δ 1.15(˜t, 8, CH₃ +NH₂), 1.39(m, 4, CH₂ CH₂), 1.56(m, 2,CH₂), 2.63(t, 2, NCH₂), 3.35-3.7(m, 4, CH₂ O), and 4.41 ppm (t, 1, CH).

ir (film): 3600-3100 (vbr), 1130, 1070 cm⁻¹.

iii) Synthesis of Acrylamidopentanal Diethyl Acetal (APDA). Thiscompound was made from 25 g (0.14 mol) of aminopentanal diethyl acetal,12.9 g of acryloyl chloride, 35 g of 14N NaOH and 65 mL of CH₂ Cl₂ usingthe same procedures as for ABDA (no pH adjustment). The product (32.5 g)had a gc retention time of 7.80 min.

nmr (CD₂ Cl₂): δ 0.91(t, 6, CH₃), 1.05(m, 2, CH₂), 1.40(m, 4, CH₂ CH₂),3.02(q, 2, NCH₂), 3.1-3.45(m, 4, OCH₂), 4.19(t, 1, CH), 5.31(m, 1,vinyl), 5.94(m, 2, vinyl), and 6.50 ppm (br.s. 1, NH).

d) N-(4,4-Diethoxybutyl)-O-vinylcarbamate (DBVC) DBVC is an example ofthe monomer of the invention containing a vinyl carbamate moiety.

This procedure is essentially the same as that for ABDA. To 95 mL of CH₂Cl₂ and 50 g of 14N NaOH in a 500 mL flask cooled to 10° C. was added37.8 g (0.235 mol) of 4-aminobutyraldehyde diethyl acetal. The mixturewas stirred vigorously while vinyl chloroformate, 25 g (0.235 mol), wasadded at a rate to maintain the reaction below 30° C. One hour after theaddition was complete, the reaction was monitored by gc, showingcomplete consumption of the amine. The final pH was 10.3. The phaseswere separated. The organic phase was washed with saturated aqueousNaCl, and the aqueous phase was back extracted with fresh CH₂ Cl₂. Thecombined organic phases were dried over anhydrous MgSO₄ and concentratedon a rotary evaporator to yield 34.5 g (63.5% yield) of a productanalyzing as 98% a single peak at 7.13 min. Vacuum distillation of a 4 gsample over Na₂ CO₃ gave 3.25 g collected at 110°-130° C./0.2 torr. Thismaterial had a gc retention time of 5.16 min (decomposition on the gc),but gave a correct nmr (CD₂ Cl₂): δ 1.15(t, 6, CH₃), 1.60(m, 4, CH₂CH₂), 3.18(q, 2, NCH₂), 3.25-3.7(m, 4, OCH₂), 4.36(d, 1, vinyl), 4.45(t,1, CH), 4.67 (dd, 1, vinyl), 5.56(brs, 1, NH), 7.18(dd, 1, vinyl)

e) Crotonamidobutyraldehyde diethyl acetal (CBDA) CBDA is an example ofa monomer of the invention containing the crotonamide moiety having theolefinic unsaturation.

This reaction was run as with DBVC (Example 15d) with 80.5 g (0.5 mol)of AmBDA, 52.2 g of crotonoyl chloride, 200 mL of CH₂ Cl₂ and 100 g of14N NaOH. The final product was adjusted to pH 10.5 with dilute HOAc andworked up as above to yield 97 g of clear yellow oil. By gc, 88% of thetotal had a retention time of 4.46 min. Kugelrohr distillation of 5 ggave 4.95 g of lighter colored product at 150°-160° C. bath temperature(0.22 torr), nmr (CD₂ Cl₂): δ: 1.17(t, 6, CH₃), 1.59(m, 4, CH₂ CH₂),1.82(dm, 3, CH₃ C═), 3.25(m, 2, NCH₂), 3.35-3.7(m, 4, OCH₂), 4.43(˜t, 1,CH), 5.84(dm, 1, vinyl), 6.31(bs, 1, NH) and 6.73 ppm(dq, 1, vinyl).

f) Cinnamidobutyraldehyde diethyl acetal (DEBC) DEBC is an example of acinnimamide moiety containing polymerizable monomer of the invention.

Cinnamoyl chloride, 55 g (0.33 mol) was added slowly to a cooled twophase mixture of aminobutyraldehyde diethyl acetal, 53.1 g (0.33 mol),132 mL of CH₂ Cl₂ and 65 g of 14N NaOH. The product partly precipitatedfrom CH₂ Cl₂. Work-up (aqueous phase separation, back extraction withCH₂ Cl₂, concentration at low pressure) gave 110 g of a crude solid, mp45°-47° C. showing as the major product (>90%) by gc a compound at 9.16min. Attempted kugelrohr distillation produced sample decompositionabove 200° C.

nmr (DMSO-d₆): δ 1.10(t, 6, CH₃), 1.50(m, 4, CH₂ CH₂), 2.50(sh. m,DMSO-d₅), 3.16(˜t, 2, CH₂ N), 3.3-3.6(m, 4, CH₂ O), 4.44(˜t, 1, CH),6.64(d, 1, J=16 Hz, vinyl) and 7.2-7.6 ppm (m, 6, vinyl and aromatic).

ir (solid film): 3270, 1655, 1620, 1550, 1455, 1345, 1230, 1130, 1065cm⁻¹.

g) N-allyl-N'-(diethoxyethyl)urea (ADEEU) ADEEU is a monomer accordingto the invention which contains a urea moiety and can be cyclized byacidic cure to a 5-membered cyclic urea.

Allylisocyanate (16.6 g, 0.2 mol) was added slowly to a rapidly stirredice cooled two-phase mixture of 26.6 g (0.2 mol) of aminoacetaldehydediethyl acetal, 70 mL of CH₂ Cl₂ and 40 g of 14N NaOH. A smalladditional sample of isocyanate was postadded to complete amineconversion. Work-up as for ABDA and concentration over Na₂ CO₃ gave 32.2g (80% yield) of a product composed 99.5% of a single peak at retentiontime 7.83 min.

nmr (CD₂ Cl₂): δ 1.18(t, 6, CH₃), 3.23(t, 2, CH₂ N), 3.8-3.4(m, 4,OCH₂), 3.73(m, 2, allyl), 4.45(t, 1, CH), 5.06(dm, 1, J=10 Hz, vinyl),5.15(dm, J˜18 Hz, vinyl), 5.66(br.t, 1, NH) and ˜5.8 ppm (m+br.t, 2, NH,vinyl).

ir (film): 3340, 1635, 1570, 1260 (br), 1130, 1060 cm⁻¹.

h) Acrylamidobutyraldehyde dimethyl acetal (ABDA-Me) ABDA-Me is thedimethylacetal derivative of ABDA.

i) Synthesis of Aminobutyraldehyde Dimethyl Acetal (AmBDA-Me). Thisreaction was run as for aminopentanal diethyl acetal [Example 15(c)(ii)]using MeOH as solvent (160 mL), 7.8 g of Raney nickel and 25 g (0.194mol) of cyanopropionaldehyde dimethyl acetal. (H₂ consumption 113% oftheoretical after 3.5 hr.) The product after concentration at reducedpressure analyzed as an essentially pure single component at 3.40 min bygc (20 g, 77.5% yield).

nmr (CD₂ Cl₂): δ 1.05(s, 2, NH₂), 1.3-1.7(2 m's, 4, CH₂ CH₂), 2.64(t, 2,CH₂ N), 3.26(s, 6, CH₃), and 4.32 ppm (˜t, 1, CH).

ir (film): 3360(s, br), 3300(s, br), 1600(m, br), 1450(s), 1375(d, s),1125(s), 1060(s, br), no CN at 2250 cm⁻¹.

ii) Synthesis of Acrylamidobutyraldehyde Dimethyl Acetal (ABDA-Me).Using the standard procedure for ABDA-Et, 16.5 g (0.124 mol) of theabove aminobutyraldehyde dimethyl acetal was reacted with 11.2 g (0.124mol) of acryloyl chloride in 40 mL of CH₂ Cl₂ /30 g of 14N NaOH. Theproduct mixture was adjusted to pH 10.0 and worked up as usual to yield16 g of oil showing predominantly a single component by gc at 7.00 min.

Anal. Calc'd for C₉ H₁₇ NO₃ ; C, 57.73; H, 9.15; N, 7.47; Found: C,57.54; H, 9.26; N, 7.35.

nmr (CD₂ Cl₂): δ 1.59(m, 4, CH₂ CH₂), 3.29(s+m, 8, CH₃, NCH₂), 4.33(˜t,1, J˜5.3 Hz, CH), 5.58(dd, 1, J=3.1 Hz, J=8.4 Hz, vinyl), 6.11(˜dd, 1,J=16.9 Hz, J=8.4 Hz, vinyl), 6.18(˜d, J=3.1 Hz, J=16.9 Hz, vinyl) and6.3 ppm (br, 1, NH).

ir (film): 3295, 1660, 1625, 1550, 1135, 1060 (br) cm⁻¹.

i) N-vinylsulfonyl-2-ethoxypyrrolidine (VSEP). To a vigorously stirredmixture of 25.7 g (0.158 mol) of 2-chloroethanesulfonyl chloride in 100mL of CH₂ Cl₂ was slowly added a mixture of 25.4 g (0.158 mol) ofaminobutyraldehyde diethyl acetal, 35 g (0.34 mol) of triethylamine and50 mL of CH₂ Cl₂. The temperature was maintained below 10° C. Stirringwas continued for 2 h. The solution was filtered to remove solid Et₃NHCl and extracted with 10 mL of 10% HCl (pH 3.0), then 10 mL of 4%NaHCO₃. The organic layer was dried with MgSO₄ and concentrated on arotary evaporator to yield 25.7 g of brown liquid containing one majorand one significant minor component by gc (˜78% at 10.83 min, 8% at 9.12min). Distillation of an aliquot on a kugelrohr apparatus (130° C., 0.5torr) increased the ratio of the short retention time peak.

nmr (CD₂ Cl₂, undistilled) δ 1.19(t, 3, CH₃), 1.5-2.2(m 4, CH₂ CH₂),3.8-3.1(m, 4, OCH₂, NCH₂), 5.03(d, 1, J=4.5 Hz, NCHO), 5.96(d, 1, J=9.5Hz, vinyl), 6.19(d, 1, J=16.4 Hz, vinyl), and 6.41 ppm (dd, 1, J=9.5 Hz,J=16.4 Hz, vinyl).

ir (film); no NH, 1345(s), 1165(s), 1012, 735 cm⁻¹.

j) 1-Allyl-6-ethoxy-4-methylhexahydropyrimidin-2-one (AEMHP). Followinga related procedure, [G. Zigeuner, W. Rauter, Monatshefte fur Chemie,96, 1950 (1965)], allylurea (24.5 g, 0.25 mol), crotonaldehyde (19.67, g0.29 mol) and 37% HCl (12 drops) were mixed with 140 g of EtOH at roomtemperature for 3 d, during which all of the crotonaldehyde wasconsumed. The major product had a retention time near that of allylurea.The dark mixture was neutralized with Na₂ CO₃, filtered and concentratedat reduced pressure. Part of the crude mixture was extracted withcyclohexane, decolorized with charcoal, filtered and concentrated togive a light yellow oil which produced white crystals (mp 72°-16° C.) onstanding. A separate sample was submitted to kugelrohr distillation(0.05 torr) to give further products: E at 90° C., F at 145°-155° C.(solid, mp 72°-76° C.) and G at 145°-155° C. (liquid).

nmr (CD₂ Cl₂): δ 1.16(d, 3, J=6.5 Hz, CH₃), 1.18(t, 3, J=6.8 Hz, CH₃),1.45(ddd, 1, J=13.7 Hz, J=12.1 Hz, J=2.9 Hz, CHH'), 2.01(dm, 1, J=13.7Hz, J˜2.4 Hz, CHH'), 3.49(q, 1, J=6.7 Hz, CHH'O), 3.50(q, 1, J=6.7 Hz,CHH'O), 3.8-3.5(m, 2, CHN, allyl), 4.38(ddt, 1, J=18.0 Hz, J=4.4 Hz,J˜1.7 Hz, allyl), 4.49(t, 1, J˜2.6 Hz, NCHO), 4.81(br.s, 1, NH), 5.08(t,1, J˜1.7 Hz, vinyl), 5.14(dq, 1, J=6.1 Hz, J˜1.4 Hz, vinyl), and 5.80ppm (m, 1, vinyl). Sample E was similar, but contained more signals,indicating a mixture of epimers.

ir (8074-15, solid film): 3200 (br), 1640, 1505, 1425 (br), 1350 cm⁻¹.

k) N-Allyl-N'-Butyraldehyde Diethyl Acetal Melamines and Ammelines. Theexample demonstrates the preparation of melamine derivatives. Cyanuricchloride, 18.4 g (0.1 mol) was dissolved in 125 ml of CH₂ Cl₂ and addedto 300 ml of ice/water and stirred mechanically. Allylamine, 5.7 g (0.1mol), in 100 ml of H₂ O containing 10.6 g (0.1 mol) of Na₂ CO₃ was addedover 30 min while maintaining a 0°-5° C. temperature range. Allylamineconversion was complete by gc. At the same temperature 32.2 g (0.2 mol)of aminobutyraldehyde diethyl acetal in 150 ml of water containing 21 g(0.2 mol) of Na₂ CO₃ was added. The mixture warmed to room temperatureover 90 min and was then heated at reflux for 2 h, but amine conversionremained incomplete. The reaction mixture was separated and the aqueouslayer was back extracted with CH₂ Cl₂. The combined organic fractionswere concentrated under reduced pressure to give a white solid. This wasrecrystallized, giving 43 g of fraction 1, mp 153°-154° C., from MeOHand 0.7 g of fraction 2, mp 143°-144° C., from hexane.

nmr(CD₂ Cl₂) fxn 1: δ 1.07(2t, 6, CH₃), 1.66(m, ˜5, CH₂, OH?),3.7-3.3(m, 6, OCH₂, NCH₂), 4.04(m, 2, allyl), 4.47(m, 1, CH), ˜5.21(dm,1, J˜18 Hz, vinyl), ˜5.14(dm, 1, J˜12 Hz, vinyl), ˜5.4, 5.6, 5.8(br.m's,1-2, NH), and ˜5.9(m, ˜1, vinyl). fxn 2: identical chemical shifts,integral ratios approximately 6:4.6:6:1.1:0.9:1.4:2(δ5.4-6.0).

ir(solid film): 3250(br), 3090(br), 1638, 1550(s), 1409, 1130, 1105,1065(br), 990, 802 cm⁻¹.

Fraction 1 is most likely the Ammeline 1 and 2 probably contains 1 andthe desired 2. The presence of both an allyl and an amine/blockedaldehyde is clear, however.

l) N-Allylglyoxylamide Diethyl Acetal (AGDA). Allylamine, (32 g, 0.57mol) and ethyl diethoxyacetate (100 g, 0.57 mol) were heated at 105° C.with 1 g each of NaOEt and imidazole as catalysts. After 28 h anadditional 16 g of allylamine was added. At 52 h a small amount oforange solid, mp 140°-148° C. was filtered off and the mixture wasdistilled on a kugelrohr apparatus (1.7 torr, 105°-115° C.). Thedistillate was composed of 0.8 g of white solid mp 110°-113° C. and 75 g(70.6%) of N-allylglyoxamide diethyl acetal. After several weeksrefrigeration, 5 g of additional precipitate separated from the sample.This was recrystallized from hexane to give a white solid identified asN,N'-diallyloxamide, mp 158°-159° C.

AGDA: IR (film): 3300, 1670, 1530 (vinyl) cm⁻¹ ; ¹ H NMR (CDCl₃): δ6.8(br s, 1, NH), 5.7-6.0 (m, 1, vinyl), 5.1-5.3 (2dm, 2, vinyl), 4.82 (s,1, methine), 3.96 (apparent tt, J=5.9 Hz, allyl), 3.67 (m, overlappingq, 4, OCH₂) and 1.28 (t, 6, CH₃).

Diallyloxamide: IR (film): 3320, 1615, 1530 cm⁻¹, ¹ H NMR (CDCl₃): δ7.55(br s, 2, NH), 5.84 (m, 2, vinyl), 5.13-5.30 (2dm, 4, vinyl), 3.94(apparent tt, 4, J=5.9 Hz, allyl) GC/MS: m/e 168, 153, 126, 84, 51, 56,41 CI (NH₃): m/e 186 (m+18).

GC Analysis

Most gas chromatographic analyses were done on a Hewlett-Packard 5380gas chromatograph using a 42 ft and a 12 m OV-101 capillary column,split ratio 200:1, column flow approximately 1 ml/min and using thefollowing programs:

a. 65°/2 min, then 65°→250° at 25°/min

b. 150°/2 min, then 150°→250° at 15°/min

c. 65°/2 min, then 65°→250° at 15°/min

d. 70°/2 min, then 70°→250° at 15°/min

e. 150°/2 min, then 150°→300° at 15°/min.

A few runs were also done on a 30 m wide bore DB-5 (60:1 split ratio) ora 30 m DB-17 column.

EXAMPLE 16 Vinyl Acetate/Ethylene/ABDA (6%) Emulsion Polymer Synthesis,Continuous Comonomer Addition.

A 1 gal reactor was charged with 42.8 g of vinyl acetate, 14.3 g ofIgepal CO-887, 10.0 g of Igepal CO-630, 10.0 g of Pluronic F-68, 10.0 gof Pluronic L-64, 857 g of a 2% aqueous solution of Natrosol 250 GR,47.0 g of deionized water, 4.1 g of sodium acetate, 0.05 g of ferricammonium sulfate, 3.02 g of acetic acid, and 11.4 g of a 10% aqueoussolution of sodium formaldehyde sulfoxylate (SFS) and purged for 40 minwith nitrogen. The mixture was heated to 48° C., agitated at 800 RPM,pressurized with ethylene to 450 psi and initiated by adding a solutionof 14 g of potassium persulfate and 47 g of sodium acetate in 981.3 g ofwater at 0.6 mL/min. Upon initiation, the rate of catalyst addition wasswitched to automatic control and 984.7 g of vinyl acetate was added at6.3 mL/min and 370 g of a 20% aqueous solution of ABDA was added at 1.8mL/min. One hour after the start of catalyst addition, a 10% aqueoussolution of SFS was pumped in at 0.2 mL/min. The reaction temperaturewas maintained at 49° C. and the pressure at 460 psi. After three h thevinyl acetate had been added and the ethylene makeup was shut off.Thirty min later the ABDA had been added. The catalyst and activatorsolutions were added for an additional 30 min. The reaction was cooled,degassed and treated with 5 g of a 10% aqueous solution of t-butylhydroperoxide and 4.6 g of a 50% aqueous solution of colloid defoamer.The resulting emulsion had 44.4% solids, pH 4.52 and a viscosity of 1080cps.

EXAMPLE 17 PVOH/g-VAc/ABDA (19/76/5 Ratio), Continuous FunctionalComonomer Addition

A 2 L reactor was charged with 300 g of a 20% aqueous solution of PVOH(Vinol 205), 210 g of deionized water and 15 g of vinyl acetate andpurged for 45 min with nitrogen. The kettle was heated to 55° C. and thereaction was initiated by adding two solutions (one a 2.5% aqueoussolution of hydrogen peroxide and the other a 2.5% aqueous solution ofascorbic acid) at a rate of 0.34 mL/min. Upon initiation, a solution ofof 15 g ABDA in 225 g of vinyl acetate was added at a rate of 2.5mL/min. The jacket was cooled to maintain a reaction temperature of 56°C. A free monomer level of 1.3% was maintained. The reaction wascomplete after 2.25 h to give a 37% solids emulsion, pH 5.43, viscosity11,640 cps.

EXAMPLE 18 PVOH/g-VAc/ABDA, (19/76/5 Ratio), Comonomer Addition at theEnd

A 2 L reactor was charged with 300 g of a 20% aqueous solution of Vinol205, 210 g of deionized water, and 225 g of vinyl acetate and purged for45 min with nitrogen. The kettle was heated to 55° C. and the reactionwas initiated by adding two solutions (one a 2.5% aqueous solution ofhydrogen peroxide and the other a 2.5% aqueous solution of ascorbicacid) at a rate of 0.34 mL/min. Upon initiation, the activator andcatalyst addition rates were reduced to 5.5 mL/h. The jacket was cooledto maintain a reaction temperature of 56° C. When the free monomerreached 2.0%, a mixture of 15 g of ABDA and 15 g of vinyl acetate wasadded at a rate of 2.3 mL/min. The reaction was complete after 1.25 h togive a 35.4% solids emulsion, pH 5.32, and viscosity 2160 cps.

EXAMPLE 19 PVOH/g-VAc/ABDA (19/76/5 Ratio), Trail Addition of Comonomer

A 2 L reactor was charged with 300 g of a 20% aqueous solution of Vinol205, 210 g of deionized water and 15 g of vinyl acetate and purged for45 min with nitrogen. The kettle was heated to 55° C. and the reactionwas initiated by adding two solutions (one a 2.5% aqueous solution ofhydrogen peroxide and the other a 2.5% aqueous solution of ascorbicacid) at a rate of 0.34 mL/min. Upon initiation the activator andcatalyst addition were slowed to 5.5 mL/h and 30 g of vinyl acetate wasadded at 2.15 mL/min. When the vinyl acetate had been added, a mixtureof 2.65 g of ABDA in 195 g of vinyl acetate was added at 2.15 mL/min.When this had been added, 11.8 g of a 20% aqueous solution of ABDA wasadded at the same rate. The jacket was cooled to maintain a reactiontemperature of 55° C. The free monomer level was maintained atapproximately 0.8%. The reaction was complete in 1.5 h. Solids: 34.4%,pH: 4.81, viscosity: 3800 cps.

EXAMPLE 20 VAc/ABDA (90/10), Continuous Comonomer Addition

A 2 L reactor was charged with 30 g of vinyl acetate, 200 g of a 2%aqueous solution of Natrosol 250 GR, 3.08 g of Igepal CO-887, 2.16 g ofIgepal CO-630, 2.16 g of Pluronic F-68, 2.16 g of Pluronic L-64, and 272g of deionized water and purged for 45 min with nitrogen. The kettle washeated to 55° C. and the reaction was initiated by adding two solutions(one a 2.5% aqueous solution of hydrogen peroxide and the other a 2.5%aqueous solution of ascorbic acid) at a rate of 0.34 mL/min. Uponinitiation, the activator and catalyst addition rates were slowed to 5.5mL/h and a mixture of 30 g of ABDA in 240 g of vinyl acetate was addedat 2.15 mL/min. The jacket was cooled to maintain a reaction temperatureof 55° C. and the free monomer was maintained at about 1.4%. Thereaction was complete in 1.5 h. Solids: 33.3%, pH: 2.98, viscosity: 860cps.

EXAMPLE 21 PVOH/g-VAc/E/ABDA 9/86/E/5 Ratio Emulsion Polymer Synthesis,Continuous Comonomer Addition

A 1 gal reactor was charged with 1520 g of a 10% aqueous solution ofVinol 205, 283 g of vinyl acetate, 10 g of a 0.2% aqueous solution offerrous sulfate and 10 g of a 2.5% aqueous solution of erythorbic acidand purged for 30 min with nitrogen. The kettle was heated to 53° C.,agitated at 900 RPM, pressurized with ethylene to 900 psi (no makeup)and initiated by adding two solutions (one a 2.5% aqueous solution oferythorbic acid and the other a 2.5% aqueous solution of hydrogenperoxide) at 3.0 mL/min. Upon initiation, the catalyst and activatorflow were slowed to 0.7 mL/min.

Vinyl acetate (1130 g) was added at 3.8 mL/min and 394 g of a 20%aqueous solution of ABDA (with 2.0 g of Igepal CO-887 added) was addedat 1.3 mL/min. The temperature was maintained at 53° C. and the freemonomer at 4%. The monomers were added over 4.5 h. The catalyst andactivator additions were continued for an additional 30 min. Thereaction was cooled, degassed and treated with 4.6 g of a 50% aqueoussolution of Colloid 585. Solids: 41.1%, pH: 3.6, viscosity: 5740 cps.

EXAMPLE 22 PVOH/g-VAc/E/ABDA (9/86/E/5 Ratio), Comonomer Addition at theEnd

A 1 gal reactor was charged with 1,414 g of a 10% aqueous solution ofVinol 205, 263 g of vinyl acetate, 10 g of a 0.2% aqueous solution offerrous sulfate and 10 g of a 2.5% aqueous solution of erythorbic acidand purged for 30 min with nitrogen. The mixture was heated to 55° C.,agitated at 900 RPM, pressurized with ethylene to 900 psi (no makeup)and initiated by adding two solutions (one a 2.5% aqueous solution oferythorbic acid and the other a 2.5% aqueous solution of hydrogenperoxide) at 3.0 mL/min. Upon initiation, the catalyst and activatorrates were slowed to 0.70 mL/min and 1051 g of vinyl acetate was addedat 3.8 mL/min. The temperature was maintained at ˜53° C. and the freemonomer at 4.0%. After 4.25 h, 366 g of a 20% aqueous solution of ABDAwas added at 4.1 mL/min. The vinyl acetate delay was complete after fiveh and the ABDA delay after 5.5 h. The activator and catalyst solutionswere added until the 6 h mark, whereupon the reaction was cooled,degassed and treated with 4.6 g of a 50% aqueous solution of Colloid585. Solids: 41.8%; pH: 3.12, adjusted to 4.2; viscosity: 17,760 cps.

EXAMPLE 23 VAc/ABDA (6%) Emulsion Polymer, Comonomer Added at the End

A 1 gal reactor was charged with 42.8 g of vinyl acetate, 14.3 g ofIgepal CO-887, 10.0 g of Igepal CO-630, 10.0 g of Pluronic F-68, 10.0 gof Pluronic LC-64, 857 g of a 2% aqueous solution of Natrosol 250 GR,4.1 g of sodium acetate, 3.30 g of acetic acid, 0.05 g of ferricammonium sulfate, 47.0 g of deionized water and 11.4 g of a 10% aqueoussolution of SFS, and purged for 40 min with nitrogen. The mixture washeated to 48° C., agitated at 800 RPM, pressurized with ethylene to 450psi (continuous makeup) and initiated by adding a solution of 14 g ofpotassium persulfate and 4.7 g of sodium acetate in 981 g of water at0.6 mL/min. Upon initiation, the catalyst addition rate was switched toautomatic control and 985 g of vinyl acetate was added at 6.3 mL/min.One h after the start of the catalyst addition, a 10% aqueous solutionof SFS was pumped in at 0.2 mL/min. The reaction temperature wasmaintained at 48° C. and a 5° difference was maintained between thereactor and jacket temperatures. The free monomer was held at 5%. After2.25 h, 370 g of a 20% aqueous solution of ABDA was added at 3.5 mL/min.The vinyl acetate delay was complete at 3.0 h and the ethylene makeupwas then turned off. The ABDA delay was complete at 4.0 h, whereupon thefree monomer was 1.5%. The reaction was cooled, degassed and treatedwith 5 g of a 10% aqueous solution of t-butyl hydroperoxide and 4.6 g ofa 50% aqueous solution of Colloid 585. Solids: 45.8%, pH: 4.37,viscosity: 2,320 cps.

EXAMPLE 24 PVOH/g-VCl/E/ABDA (4.7/76/17.4/1), Continuous ComonomerAddition

The polymerization was carried out in a 1 gal pressure vessel equippedwith a jacket and an agitation system involving turbine blades. Inpreparing the copolymer emulsion the following initial charge wasintroduced into the reaction vessel:

    ______________________________________                                        INITIAL CHARGE                                                                ______________________________________                                        Distilled Water          555    g                                             Ferrous Ammonium Sulfate 0.9    g                                             Sequestrine 30A.sup.a    2.7    g                                             Vinol 205.sup.b PVOH (12% Solution)                                                                    854    g                                             ______________________________________                                         .sup.a Ethylenediamine tetraacetic acid sodium salt.                          .sup.b An 87 to 89 mole % hydrolyzed PVOH marketed by Air Products and        Chemicals, Inc.                                                          

The pH of the above charge was adjusted between 4.0 and 4.5 with aceticacid. The vessel contents were agitated at 200 rpm and purged threetimes with ethylene (25 psig). Vinyl chloride monomer (240 g) was thenadded and the reactor was heated to 55° C. and pressurized with ethylene(875 psig). The agitation was increased to 900 rpm and 7 mL of a 10%aqueous solution of erythorbic acid (pH 4.5) was pumped into thereactor. After the temperature and pressure had equilibrated, thepolymerization was initiated with a 1% aqueous hydrogen peroxidesolution. After the heat of polymerization output rate began todecrease, the remaining vinyl chloride monomer (1,415 g) and 105 g of a20% aqueous solution of ABDA (plus 1 g of Igepal CO887 surfactant) wereadded over a 4 h and a 43/4 h period respectively, maintaining thepolymerization temperature of 55° C. using approximately 1.2 g hydrogenperoxide as a 1% solution and 2.7 g erythorbic acid as the activator.Additional oxidant and reductant were used after the vinyl chloridemonomer had been added to complete the polymerization. A total of 1.67 gof hydrogen peroxide as a 1% solution and 5.0 g of erythorbic acid wereused for the entire polymerization. The ethylene pressure was allowed to"float" during the polymerization without makeup or withdrawal.

The emulsion was transferred to a degasser and the unreacted vinylchloride monomer reduced to less than 10 ppm by the addition of vinylacetate (15 g) followed by t-butyl hydroperoxide (4 g) and erythorbicacid (3 g), ferrous ammonium sulfate (0.2 g) and sequestrine 30A (0.8 g)in water (50 g). The vinyl chloride-ethylene copolymer was 76 wt. %vinyl chloride, 17.4 wt. % ethylene, 0.96% ABDA and had a Tg of 18.5° C.Emulsion solids were 52%, [η]=0.41 (soluble portion).

EXAMPLE 25 Vinyl Acetate/Butyl Acrylate Emulsion Polymerizations

An atmospheric emulsion polymerization was performed in a 1 L resinkettle outfitted with a double propeller agitator and reflux condenseras follows:

Kettle Charge

319 g H₂ O

0.375 g Natrosol 250 HR

9.2 g Igepal CO-887

2.15 g Igepal CO-630

0.166 g sodium formaldehyde sulfoxylate (SFS)

2.8 g 0.15% FeSO₄.7H₂ O

Monomer Delay

344 g vinyl acetate

56 g butyl acrylate

7.8 g Pluronics F-68

5.14 g Pluronics L-64

0.58 g t-butylhydroperoxide (TBHP, 70%) Additional TBHP was added tokeep the reaction going when necessary.

24 g (3%) comonomer

Activator

0.628 g SFS

0.628 g sodium benzoate

dilute to 25 mL with DI H₂ O

Chaser

0.25 g t-BHP

0.75 g DI H₂ O

The DI-H₂ O was charged to the kettle and sparged with N₂ for 30 minunder moderate agitation. The remainder of the kettle charge was addedand the mixture was heated to 65° C. Stirring speed was adjusted to givea strong vortex. Each delay was set to run for 2 h. The monomer delayrate was approximately 3.5 mL/min and the activator rate wasapproximately 0.21 mL/min, but high enough to maintain an excess ofactivator. The reaction was initiated by pumping in the monomer delay.When the kettle charge became bluish white (within 10 min), theactivator was turned on. The temperature was held at 65°-70° C. duringthe run. Percent free monomer was measured at hourly intervals by KBrO₃titration. After all of the monomer delay had been added and the percentunreacted VAc fell below 1%, the chaser was added to bring the VAc downto ≦0.5%. The vinyl acetate/butyl acrylate/3% ABDA copolymer emulsionhad a pH 5.6 and 50% solids.

EXAMPLE 26 VAc/ABDA (90/10) Continuous Comonomer Addition

A 2 L reactor was charged with 30 g of vinyl acetate, 200 g of a 2%aqueous solution of Natrosol 205GR, 3.08 g of Igepal CO-887, 2.16 ofIgepal CO-630, 2.16 g of Pluronic F-68, 2.16 g of Pluronic L-64, and 272g of deionized water and purged for 45 min with nitrogen. The kettle washeated to 55° C. and the reaction initiated by adding two solutions (onea 2.5% aqueous solution of hydrogen peroxide and the other a 2.5%aqueous solution of ascorbic acid) at a rate of 0.34 mL/min. Uponinitiation, the activator and catalyst additions were slowed to 5.5 mL/hand a solution of 30 g of ABDA in 240 g of vinyl acetate was added at2.15 mL/min. The reaction was maintained at a temperature of 55° C. anda free monomer of 1.4%. The reaction was complete in 1.5 h.

EXAMPLE 27 VAc/AEP (90/10) End Comonomer Addition

A 2 L reactor was charged with 542 g of deionized water, 0.37 g ofNatrosol 250HR, 9.2 g of Igepal CO-887, 2.15 g of Igepal CO-630, 2.8 gof aqueous ferrous sulfate heptahydrate (0.15% solution) and 0.16 g ofsodium formaldehyde sulfoxylate and purged for 45 min with nitrogen. Thekettle was heated to 65° C. and the reaction was initiated by adding asolution of 288 g of vinyl acetate, 5.9 g of Pluronic F-68, 4.1 g ofPluronic L-64 and 0.46 g of t-butyl hydroperoxide (70%) at a rate of 2.8mL/min. Five min after initiation, a solution of 0.63 g of SFS, 0.63 gof sodium benzoate and 50.5 g of deionized water was added at 0.34mL/min. When the monomer delay was complete, a solution of 72 g of vinylacetate, 1.4 g of Pluronic F-68, 1.04 g of Pluornic L-64, 0.12 g oft-butyl hydroperoxide (70%) and 40 g of AEP was added at the same rate.Fifteen min after all the delays had finished a solution of 0.5 g oft-butyl hydroperoxide (70%) in 1.5 g of deionized water was added. Thereaction was complete within 30 min.

EXAMPLE 28 VAc/BA/AEP, End Comonomer Addition

A 2 L rector was charged with 542 g of deionized water, 0.37 g ofNatrosol 250HR, 9.2 g of Igepal CO-887, 2.15 g of Igepal CO-630, 0.156 gof sodium formaldehyde sulfoxylate and 2.8 g of aqueous ferrous sulfateheptahydrate (0.15% solution). It was then purged for 45 min withnitrogen. The kettle was heated to 65° C., and the reaction wasinitiated by adding 330 g of a solution comprised of 344 g of vinylacetate, 56 g of butyl acrylate, 7.29 g of Pluronic F-68, 5.4 g ofPluronic C-64 and 0.58 g of 70% TBHP at a rate of 2.8 mL/min. Ten minafter initiation, a solution of 0.63 g of SFS, 0.63 g of sodium benzoateand 50.5 g of deionized water was added at 0.34 mL/min. When the monomerdelay was complete, a solution comprised of 82.6 g of the initialmonomer delay and 40 g of AEP was added at the same rate. Fifteen minafter the delays had finished, a solution of 0.5 g of TBHP (70%) in 1.5g of deionized water was added. The reaction was complete within 30 min.

EXAMPLE 29 VAc/BA/AEP, Continuous Comonomer Addition

A 2 L reactor was charged with 542 g of deionized water, 0.37 g ofNatrosol 250 HR, 9.2 g of Igepal CO-887, 2.15 g of Igepal CO-636, 0.156g of SFS and 2.8 g of aqueous ferrous sulfate heptahydrate (0.15%solution). The kettle was purged for 45 min with nitrogen and heated to65° C. The reaction was initiated by adding a solution of 344 g of vinylacetate, 56 g of butyl acrylate, 40 g of AEP, 7.2 g of Pluconic F-68,5.14 g of Pluconic C-64, and 0.58 g of TBHP (70%) at a rate of 2.8mL/min. Seven min after initiation a solution of 6.63 g of SFS, 0.63 gof sodium benzoate and 50.5 g of deionized water was added at 0.34mL/min. Fifteen min after all the delays were finished, a solution of0.5 g of TBHP (70%) in 1.5 g of deionized water was added. The reactionwas complete within 30 min.

EXAMPLE 30 VAc/BA/ABDA, Trail Comonomer Addition

This reaction was performed as in Example 28 except that when the firstmonomer delay was completed, a solution comprised of 82.6 g of theinitial monomer delay and 20 g of ABDA was added at the same rate,followed by 9.5 g of pure ABDA. Fifteen min after all of the delays hadbeen added, a solution of 0.5 g of TBHP (70%) in 1.5 g of deionizedwater was added. Reaction was complete within 30 min.

EXAMPLE 31 BA/MMA/ABDA

A 2 L reactor was charged with 752 g of deionized water and 48 g ofTriton X-200 and purged for 45 min with nitrogen. A solution of 191 g ofbutyl acrylate, 169 g of methyl methacrylate (MMA), 40 g of ABDA, 8 g ofaqueous ferrous sulfate heptahydrate (0.15% solution) and 2 g ofammonium persulfate was added and the mixture was stirred for 30 min.Then 2.0 g of sodium meta-bisulfite and 10 drops of TBHP (70%) wereadded. The reaction temperature rose over 12 min to 50° C. and thendropped. When the temperature reached 25° C., the reaction was complete.

EXAMPLE 32 VAc/DBMA, End Comonomer Addition

A 2 L reactor was charged with 468 g of deionized water, 3.08 g ofIgepal CO-887, 2.16 g of Igepal CO-630, 2.16 g of Pluronic F-68, 2.19 gof Pluronic C-64, 4.0 g of Natrosol 250 GR and 30 g of vinyl acetate.The kettle was purged for 45 min with nitrogen and heated to 55° C. Thereaction was initiated by adding a 2.5% aqueous solution of ascorbicacid and a 2.5% aqueous solution of hydrogen peroxide on demand bytemperature. Five min after initiation, 225 g of vinyl acetate was addedat a rate of 2.3 mL/min followed by a solution of 15 g of vinyl acetateand 18 g of DBMA. After 4.5 h, the free monomer was less than 1.5% andthe reaction was complete.

EXAMPLE 33 VAc/BA/ABDA/BA Chaser

This reaction was a repeat of Example 28 except that the first monomerdelay employed only 40 g of butyl acrylate. When the first delay wascompleted, a solution comprised of 79.4 g of the initial monomer delayand 15 g of ABDA was added at the same rate, followed by 16 g of butylacrylate. Fifteen min after all the delays had finished, a solution of0.5 g of TBHP (70%) in 1.5 g of deionized water was added. The reactionwas complete within 30 min.

EXAMPLES 34-49 Swell Index and Percent Solubles Measurements on Emulsionand Solution Polymers

Polymer films were cast on Mylar film at 25% solids with various postadditives. The films were air dried (16-48 h) then cured for 3 and 10min at 150° C. A convected oven (oven 1) was used unless otherwiseindicated. Oven 2 was not convected. Small samples (50-100 mg) of filmwere weighed, soaked in dimethylformamide (DMF) for 1 h, brieflypat-dried and reweighed in an A1 weighing pan. The samples were thenredried at 150° C. (20 torr) or 170° C., 1 atm for 30 min. ##EQU1##

See Table 1A for additional vinyl acetate/ethylene copolymer emulsionsprepared generally following the procedure of Example 16.

Table 1B gives additional vinyl acetate/butyl acrylate copolymeremulsions prepared generally following the procedure of Example 25.

Table 2 provides vinyl acetate copolymer emulsions prepared generallyfollowing the procedure of Examples 26 or 27.

Tables 1A, 1B and 2 also include swell index and percent solubles datawhich show that copolymers incorporating the acetal and hemiamidalcopolymers of the invention can be cross-linked.

    __________________________________________________________________________    X-Linker                          Swell Index (DMF)                                                                             % DMF Solubles              Example                                                                            (molarity)                                                                              Catalyst         pH                                                                              3 min cure.sup.1                                                                      10 min cure.sup.1                                                                      3 min                                                                              10                                                                                color             __________________________________________________________________________    A .105                                                                             5% NMA    H.sub.3 PO.sub.4 3.0                                                                             2.9     2.9      15   10  C                      (0.5M)    1% PTSA            2.5     2.3       7    7  LY                     continuous.sup.6                                                                        1% NH.sub.4 Cl     4.3     4.1       8   10  LY                34   None      1% PTSA            ∞ ∞  100  100 LY                35   3% ABDA   H.sub.3 PO.sub.4 3.0                                                                             15.4    15.6     24   15  Y                      (0.14M)   1% PTSA            8.9     6.8      11    8  Y                      continuous                                                                              1% PTSA + 1% PVOH  6.7     6.3       9    9  Y                 36   6% ABIDA  H.sub.3 PO.sub.4 3.0                                                                             12.6    11.6     23   17  Y                      (0.28M)   H.sub.3 PO.sub.4 + 1% PVOH                                                                     2.5                                                                             12.1    9.5      15   11  LY                     continuous                                                                              1% PTSA            8.9     6.8      11    8  Y                                1% NH.sub.4 Cl (.19M)                                                                            6.2     5.8       8    7  LY                               1% NaHSO.sub.4   2.1                                                                             9.9     6.8       9    6  Y                                1% Maleic acid   2.4                                                                             13.8    12.7     19   18  LY                               1% (CO.sub.2 H).sub.2                                                                          2.0                                                                             10.9    9.4      16   12  Y                 37   9% ABDA   H.sub.3 PO.sub.4 3.0                                                                             10.6    8.9      15   12  Y                      (0.42M)   1% PTSA            6.0     4.5      10    8  Y                      continuous.sup.6                                                                        1% PTSA + 2% PVOH  4.7     4.1       8    6  Y                 38   6% ABDA   1.6% H.sub.3 PO.sub.4 (oven 2)                                                                 2.5                                                                             7.0     6.1      13    8  Y                      (0.28M)   1% PTSA (oven 2)   4.5     4.5       5    5  Y                      End.sup.6 1% PTSA + 1% PVOH (oven 2)                                                                       4.7     4.6       6    8  Y                                1% NH.sub.4 Cl (0.19M)(oven2)                                                                    4.1     3.9      10   11  LY                39   3% AEP (0.18M)                                                                          2% PTSA            9.0     9.5      34   25  Y                      end, (NH.sub.3)                                                                         2% NH.sub.4 Cl (0.28M)                                                                           10.4    9.6      30   23  Y                 40   2.5% ADBC (0.1M)                                                                        --                 ∞ (218°/1                                                                ∞ (218°/1.5                                                               100  100 LY                     cont., Tg + 9                                                                           2% PTSA            7.2     7.1       9    7  DY                     (NH.sub.3)                                                                              2% NH.sub.4 Cl (0.28M)                                                                           ∞ ∞  100  100 LY                41   2.5% ADBC --                 15 (218°/1 min)                                                                13.5 (1.5 min)                                                                         21   17  VLY                    (0.1M) cont.                                                                            1% PTSA            6.9     6.7      11   11  LY                               2% PTSA            7.7     7.0       6    9  LY                42   3% BNMA   1% NH.sub.4 Cl   1 4.7     4.5       9    9  B                      (0.19M)   1% MgCl.sub.2    1 4.7     4.7       9    8  LB                     continuous                                                               43   3% NMA    1% NH.sub.4 Cl   1 2.8     2.8       8   10  Y, B                   (0.3M)                                                                        continuous                                                               44   3% ABDA                                                                       (0.14M)   1% PTSA          1 7.0     7.1       9    8  Y                      continuous                                                                              1% NH.sub.4 Cl   1 ∞ 18       100  17  LY                45   1.2% AEP  --               2 ∞ 2.5      100  86  LY                     (0.076M)  1% PTSA          2 7.6     7.2      14   12  DB                     1.0% AM   1% PTSA + 1% PVOH                                                                              2 7.6     7.7      12   13  DB                     (0.153M)                                                                      continuous                                                               46   3% DBMA   2% PTSA          2 ∞ ∞  100  100 DY                     (0.13M)   2% PTSA + 1% PvoH                                                                              2 ∞ ∞  100  100 DT                     continuous                                                               47   2.5% ADBC 1% PTSA          2 5.4     4.9      10   10  DB                     (0.1M)    2% NH.sub.4 Cl (0.38M)                                                                         1 ∞ ∞  100  100 LY                     continuous                                                               48   5% AHP    2% PTSA          1 4.4     4.7      10    8  Y                      (0.21M)   2% NH.sub.4 Cl (0.38M)                                                                         1 5.6     4.9      22   20  LY,                    cont. (NH.sub.3)                                       B                 49   10% ABDA  2% PTSA          1 2.3     2.3      11   10  DY                     (0.47M) + 2% NH.sub.4 Cl (0.38M)                                                                         1 3.7     3.1      13   10  Y                      1% DCPA                                                                  __________________________________________________________________________

EXAMPLES 50-64 Solution Polymerizations

Table 3 sets forth solution polymerization data. Examples 50-64 wereprepared by the following method: All of the solution polymerizationswere run with 0.297 mmol comonomer per calculated g of polymer solidspremixed with the other monomer(s).

Charge

X g comonomer

(50-X) g butyl acrylate (BA)

120 g dry toluene

0.15 g 2,2'-azobisisobutyronitrile (AIBN)

The first three components were mixed at room temperature and heated at65° C. in a 250 mL round bottom flask with a magnetic stirring bar,reflux condenser and N₂ blanket. The AIBN was then added to start thereaction. Monitoring of the unreacted free monomer (butyl acrylate andcomonomer) was done by GC.

    ______________________________________                                        Retention Times (min)                                                         ______________________________________                                        butyl acrylate           2.90                                                 ABDA                     8.16                                                 AADMA                    6.07                                                 AEP                      6.51                                                 AGDA                     6.26                                                 vinyl acetate            0.88                                                 ADBC                     8.35                                                 Et-ABDA                  8.62                                                 N-(isobutoxymethyl)acrylamide (BNMA)                                                                   5.94                                                 ______________________________________                                    

In all but Example 51, additional 10 mg amounts of AIBN were added atrandom times to keep the reaction going. The temperature was alsoincreased to 75° C. when the reaction rate decreased. Most of thereactions took longer than 24 hours, with Example 64 taking 107 hours.The reactions were terminated when the free monomer fell below 0.7%.Example 61 was run half scale.

    __________________________________________________________________________    X-linker                                                                      Comonomer    Catalyst/  Swell Index.sup.1 (DMF)                                                                   % DMF Solubles                            Example                                                                            (Molarity)                                                                            Additives                                                                            Oven.sup.5                                                                        3 min cure                                                                          10 min cure                                                                         3 min                                                                             10 min                                                                             Color.sup.2                                                                       Tack.sup.3                   __________________________________________________________________________    50   --      1% Thermal                                                                           1   ∞                                                                             ∞                                                                             100 100  --  --                           51   BNMA    1% Thermal                                                                           1   2.5   2.1    5   11  --  --                                (0.3M)                                                                   52   ABDA    1% Thermal                                                                           1   2.7   1.8   41.sup.x                                                                          39.sup.x                                                                           --  --                                (0.3M)  1% Thermal                                                                           1   1.9   2.0    3   9   --  --                           53   AEP     1% Thermal                                                                           1   2.5   2.3    10  1   --  --                                (0.3M)                                                                   54   AEP     --     1   3.9   3.0    9   5   C   ST                                (0.6M)  1% Thermal                                                                           1   2.2   1.9    13  12  LY  ST                           55   AEP (0.3M)                                                                            --     1   3.4   3.1   7.2 6.7  C   T                                 +HEA (0.3M)                                                                           1% Thermal                                                                           1   2.5   2.4    18  12  LY  ST                           56   AEP (0.3M)                                                                            --     1   3.9   3.9    22  13  C   T                                 +GAE (0.3M)                                                                           1% Thermal                                                                           1   2.6   2.6    17  12  LY  N                            57   AEP     --     1   ∞                                                                             ∞                                                                             100 100  C   VT                                (0.05M) 1% Thermal                                                                           1   ∞                                                                             ∞                                                                             100 100  LY  T                            58   AEP     --     1   ∞                                                                             ∞                                                                             100 100  C   VT                                (0.1M)  1% Thermal                                                                           1   2.3   2.2    14  6   LY  T                            59   AEP (0.05M)                                                                           --     1   ∞                                                                             ∞                                                                             100 100  C   VT                                +HEA (0.05M)                                                                          1% Thermal                                                                           1   3.5   2.8    13  19  LY  T                            60   AEP (0.05M)                                                                           --     2   ∞                                                                             ∞                                                                             100 100  C   T                                 +AM (0.1M)                                                                            1% Thermal                                                                           2   3.6   3.8    16  12  LY  T                            61   Et-ABDA 1% Thermal                                                                           1   ∞                                                                             4.2   100  27  Y, DY                                                                             VT                                (0.3M)                                                                   62   AADMA   1% Thermal                                                                           1   ∞                                                                             15.4  100 --                                         (0.3M)                                                                   63   AGDA    1% Thermal                                                                           1   ∞                                                                             3.4   100  4                                         (0.3M)                                                                    64* ABDA    1% Thermal                                                                           1   1.7   1.9    56  46  Y, DY                                                                             N                            __________________________________________________________________________     *80.5% VAc, 13.1% BA, 6.4% ABDA                                          

EXAMPLES 65-82

In Examples 65-82 polymers containing copolymerized acetal andhemiamidal monomers of the invention were applied as binder emulsions onWhatman paper at 10% binder solids add-on. Ammonium chloride was addedas a curing catalyst at 1% on solids and the impregnated paper was driedand cured at 150° C. for 3 minutes. Table 4 shows the tensile strengthvalues for the bonded paper.

    __________________________________________________________________________               Crosslinker                                                                           Addition Mode                                                                           Tensile Values (pli)                             Example                                                                            Polymer                                                                             Monomer X-Linker Monomer                                                                        Dry                                                                              Wet                                                                              Perchloro                                                                           MEK                                  __________________________________________________________________________    Paper                                                                              --    --                 8.2                                                                             0.2                                                                              6.0   --                                   without                                                                       binder                                                                        VAc/Et     0%                12.5                                                                             1.0                                                                              3.5   --                                   65   VAc/BA                                                                              10% AEP Trail     11.6                                                                             3.4                                                                              4.4   3.4                                  66   VAc/BA                                                                              10% AEP Continuous                                                                              15.5                                                                             6.0                                                                              7.2   5.4                                  67   VAc/BA                                                                              10% ABDA                                                                              Trail     16.7                                                                             7.5                                                                              7.0   5.6                                  68   VAc/BA                                                                              7% ABDA Trail     10.9                                                                             4.0                                                                              5.3   3.9                                  69   BA/MMA                                                                              10% ABDA                                                                              Batch     16.3                                                                             7.4                                                                              8.8   7.3                                  70   VAc   6% DBMA Continuous                                                                               7.3                                                                             1.4                                                                              5.4   3.3                                  71   VAc   10% DBMA                                                                              Trail     14.3                                                                             2.2                                                                              7.1   2.6                                  72   VAc   3% DEBMU                                                                              Trail     17.3                                                                             5.0                                                                              6.4   4.2                                  73   VAc   3% DEEMU                                                                              Trail     17.3                                                                             6.3                                                                              7.1   4.1                                  74   VAc/BA                                                                              5% ABDA Trail     18.2                                                                             7.1                                                                              6.3   4.9                                  75   VAc   3% ABDA Continuous                                                                              17.1                                                                             5.5                                                                              8.4   3.6                                  76   VAc   5% ABMA Continuous                                                                              17.6                                                                             5.3                                                                              --    4.7                                  77   VAc   5% ABMA +                                                                             Continuous                                                                              19.9                                                                             4.5                                                                              11.5  5.7                                             19% PVOH                                                           78   VAc   6% APDA Continuous                                                                              13.0                                                                             3.3                                                                              6.9   4.5                                  79   VAc   2.5% ADEEU                                                                            Continuous                                                                              16.2                                                                             4.6                                                                              6.1   3.0                                  80   VAc   5% DBVC Continuous                                                                              17.5                                                                             5.8                                                                              6.9   3.9                                  81   VAc   5% CBDA Continuous                                                                              17.3                                                                             5.0                                                                              7.2   4.3                                  82   VAc   4% VSEP           18.5                                                                             5.4                                                                              7.2   3.6                                  __________________________________________________________________________       On Whatman 3% paper, 10% addon                                              Batch  crosslinker monomer added all up front to polymerization reaction.     Continuous  crosslinker monomer added continuously during polymerization      reaction.                                                                     Trail  crosslinker monomer added continuously during last half of             polymerization reaction.                                                 

EXAMPLE 83 Homopolymerization of AEP

AEP (50 g) was mlxed with 100 g of isopropanol, 0.3 g of tetradecane (asinternal standard) and 50 mg of azobisisobutyronitrile (AIBN) and heatedat 67° C. under nitrogen. Gas chromatographic analysis showed 53%conversion after 4 h and 99.7% after 23 h. The product was a viscoussolution, 67% solids (due to isopropanol evaporation).

EXAMPLE 84 1:1 Copolymerization of AEP with Butyl Acrylate

A mixture of 25 g each of butyl acrylate with AEP, 100 g of isopropanol,0.3 g of tetradecane and 50 mg of AIBN was reacted as in Example 83. GCmonitoring showed similar reactivity for the two monomers with 99 and99.4% conversion respectively after overnight heating.

EXAMPLE 85 Styrene/ABDA (95/5) Emulsion Copolymer Synthesis

A 2 L reactor was charged with 590 g of deionized water, 26.7 g of SteolCS-130, 17.0 g of Igepal CO-850 and 0.8 g of methacrylic acid. Thereactor was purged with nitrogen for 30 min. The kettle was heated to40° C., 126.7 g of styrene and 6.7 g of ABDA were added, and thecontents of the reactor were stirred for 15 min. Then 2.0 g of ammoniumpersulfate was added and 100 g of a 1% aqueous solution of SFS was addedat 0.34 mL/min. Initiation occurred 2 min after beginning the activatordelay. Fifteen min later a solution of 253.3 g of styrene and 13.3 g ofABDA was added at 2.84 mL/mn. Following complete monomer addition, thekettle was heated to 90° C. and treated with 5 drops of tBHP. Twenty minlater the reaction was over.

EXAMPLE 86 Styrene/N-(4,4-Diethoxybutyl)cinnamide (DEBC)(95/5) EmulsionCopolymer

Same as Example 85 except DEBC was used instead of ABDA, and initiationrequired 2.5 min.

STATEMENT OF INDUSTRIAL APPLICATION

The invention provides self- and diol reactive, formaldehyde-freecrosslinking monomers and their derived polymers suitable as binders fornonwoven products.

We claim:
 1. A copolymer emulsion comprising an aqueous colloidaldispersion of a copolymer containing 50 to 94.5 wt % vinyl acetate, 5 to40 wt % ethylene and 0.5 to 10 wt % of a monomer represented by theformula ##STR17## where R² is a C₁ -C₄ alkyl radical, whichself-crosslinks under acidic curing conditions.
 2. The copolymeremulsion of claim 1 in which R² is ethyl.
 3. The copolymer emulsion ofclaim 1 in which R² is methyl.
 4. A polymer comprising polymerized unitsof monomer represented by the following formula: ##STR18## wherein R²and R³ are a C₁ -C₄ alkyl, orR² and R³ together are a C₂ -C₄ alkylenegroup,and at least one copolymerizable monomer selected from the groupconsisting of a vinyl ester of a C₁ -C₁₈ alkanoic acid, ethylene, vinylchloride, esters of C₃ -C₁₀ alkenoic acids with C₁ -C₁₈ alkanols,styrene, and mixtures thereof, which polymer self-crosslinks underacidic curing conditions.
 5. The polymer of claim 4 in which R² and R³are both methyl or ethyl.
 6. The polymer of claim 4 which comprises 90to 99.5 wt % polymerized units of at least one copolymerizable monomer.7. The polymer of claim 6 in which R² and R³ are both methyl or ethyl.8. The polymer of claim 4 in which the copolymerizable monomer isselected form the group consisting of a vinyl ester of a C₁ -C₁₈alkanoic acid, a vinyl ester of a C₁ -C₁₈ alkanoic acid and ethylene,vinyl chloride and ethylene, esters of C₃ -C₁₀ alkenoic acids with C₁-C₁₈ alkanols, vinyl acetate and esters of C₃ -C₁₀ alkenoic acids withC₁ -C₁₈ alkanols, styrene and mixtures thereof.
 9. The polymer of claim6 in which the copolymerizable monomer is selected form the groupconsisting of a vinyl ester of a C₁ -C₁₈ alkanoic acid, a vinyl ester ofa C₁ -C₁₈ alkanoic acid and ethylene, vinyl chloride and ethylene,esters of C₃ -C₁₀ alkenoic acids with C₁ -C₁₈ alkanols, vinyl acetateand esters of C₃ -C₁₀ alkenoic acids with C₁ -C₁₈ alkanols, styrene andmixtures thereof.
 10. The polymer of claim 7 in which thecopolymerizable monomer is selected form the group consisting of a vinylester of a C₁ -C₁₈ alkanoic acid, a vinyl ester of a C₁ -C₁₈ alkanoicacid and ethylene, vinyl chloride and ethylene, esters of C₃ -C₁₀alkenoic acids with C₁ -C₁₈ alkanols, vinyl acetate and esters of C₃-C₁₀ alkenoic acids with C₁ -C₁₈ alkanols, styrene and mixtures thereof.11. A polymer comprising polymerized units of a monomer of the formula##STR19## where R is methyl or ethyl, and at least one copolymerizablemonomer selected from the group consisting of a vinyl ester of a C₁ -C₁₈alkanoic acid, a vinyl ester of a C₁ -C₁₈ alkanoic acid and ethylene,vinyl chloride and ethylene, esters of C₃ -C₁₀ alkenoic acids with C₁-C₁₈ alkanols, vinyl acetate and esters of C₃ -C₁₀ alkenoic acids withC₁ -C₁₈ alkanols, styrene and mixtures thereof, which polymerself-crosslinks under acidic curing conditions.